TW202132919A - Negative photosensitive resin composition, and method of manufacturing polyimide and cured relief pattern by using the same having good adhesion to sealing materials, such as modeling resin, good uniformity and crack resistance for in-plane at multilayers, and excellent elongation - Google Patents

Abstract

A purpose of the disclosure is to provide a photosensitive resin composition having good adhesion to sealing materials, such as modeling resin, good uniformity and crack resistance for in-plane at multilayers, and excellent elongation after the reliability test, and also provide a method of forming a cured relief pattern by using the photosensitive resin composition. The disclosure provides a negative photosensitive resin composition, which comprises: (A) a polyimide precursor having a structural unit represented by the general formula (1), (B) a compound containing at least one selected from a urethane bond and a urea bond, (C) a photopolymerization initiator, and (D) at least one solvent selected from a 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide In the formula, X1, Y1, n1, R1 and R2 are defined in the specification.

Description

Negative photosensitive resin composition, and manufacturing method of polyimide and hardened embossed pattern using the same

The present invention relates to a photosensitive resin composition, especially a negative photosensitive resin composition, and a method for producing polyimide and hardened relief patterns using the same.

Previously, insulating materials for electronic parts, passivation films, surface protection films, and interlayer insulating films for semiconductor devices used polyimide resins and polybenzoxazole resins that have excellent heat resistance, electrical properties, and mechanical properties. , Phenolic resin, etc. Among these resins, those provided in the form of a photosensitive resin composition can easily form a heat-resistant embossed pattern film by coating, exposing, developing, and curing the composition by using the composition. Such a photosensitive resin composition has the feature of being able to significantly shorten the steps compared with the previous non-photosensitive materials.

On the other hand, in recent years, the method (package structure) of packaging a semiconductor device on a printed wiring board has also changed from the viewpoint of improving the integration degree and computing function, and reducing the chip size. There are various methods for semiconductor packaging of semiconductor devices. As a semiconductor packaging method, for example, there is a packaging method in which a semiconductor chip is covered with a sealing material (molding resin) to form an element sealing material, and then a rewiring layer electrically connected to the semiconductor chip is formed. In addition, compared with the previous packaging methods using metal pins and lead-tin eutectic soldering, other methods such as BGA (Ball Grid Array), CSP (Chip Size Packaging), SiP, etc. that can achieve higher density packaging have begun to be used. As shown, the structure where the polyimide film is directly in contact with the solder bumps.

In recent years, fan-out (fan-out) semiconductor packaging techniques have become mainstream among semiconductor packaging techniques. In the fan-out semiconductor packaging method, the semiconductor chip is first covered with a sealing material, thereby forming a chip encapsulation body that is larger than the chip size of the semiconductor chip. Then, a rewiring layer is formed in the region of the semiconductor wafer and the sealing material. In the fan-out semiconductor packaging method, the rewiring layer is formed with a thinner film thickness. Since the rewiring layer is formed in the area of the sealing material, the number of external connection terminals can be increased.

For example, as a fan-out (FO) type semiconductor device, a device described in Patent Document 1 below is known. In addition, as a photosensitive resin composition capable of cyclizing (curing) a polyimide precursor at a low temperature, a photosensitive resin composition described in Patent Document 2 is known.

In the encapsulation structure that requires the formation of a multilayer film such as the above-mentioned FO, a photosensitive resin composition is further coated on the interlayer insulating resin and the Cu wiring. According to Patent Document 3, by forming a multilayer film using a resin layer having specific physical properties, a laminate having excellent adhesion between resins can be obtained. In addition, Patent Document 4 discloses a photosensitive resin composition comprising a polyimide precursor for interlayer insulating film use, a photopolymerization initiator, and a low-molecular compound having a predetermined structure. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-129767 [Patent Document 2] International Publication No. 2019/189110 [Patent Document 3] International Publication No. 2017/146152 [Patent Document 4] Japanese Patent Laid-Open No. 2019-185031

[The problem to be solved by the invention]

For fan-out semiconductor devices, in order to prevent wafer warpage in the process, it is expected that the hardening temperature (thermal imidization temperature) will be lowered. However, if the temperature of the thermal imidization treatment is lowered, there is a problem in that the adhesion between the sealing material such as a mold resin and the rewiring layer decreases. In addition, when the rewiring layer is composed of two or more layers, there are problems such as easy loss of in-plane uniformity and cracks in the first layer. In addition, regarding the photosensitive resin composition containing the thermal alkali generator described in Patent Document 2, there are problems such as insufficient solution to the above-mentioned problems, and further reduction in storage stability. Furthermore, it can be seen that if two or more hardened embossed patterns are laminated using the previous photosensitive resin composition described in Patent Document 4, the hardened embossed pattern of the photosensitive resin composition has low wettability, and therefore When the photosensitive resin composition is further applied to the cured relief pattern, the in-plane uniformity is insufficient.

Furthermore, when forming a bump structure in which the polyimide film directly contacts the solder bumps, the polyimide film needs to have high heat resistance and chemical resistance. If it is a resin composition without heat resistance , When packaged together with the semiconductor chip on the substrate after the reflow step, a cured film with lower heat resistance will be produced. The cured film with low heat resistance will degas and shrink due to temperature changes, which will easily cause cracks and peeling.

Recently, the demand for thermosetting materials (low-temperature hardening materials) that can achieve low-temperature hardening treatment continues to increase. As a low-temperature curing material for insulating film applications, various phenol resins have been developed, but in terms of chemical resistance and heat resistance, it is desirable to use polyimide resins. In order to harden the polyimide resin, which is usually processed at 300～400℃, at low temperature, in general, a compound that promotes the imidization is added for chemical imidization, or soluble polyimide is used. amine.

On the other hand, if the heat treatment is performed at a low temperature, many low-molecular compounds will remain in the cured film, and the interaction between the resins will be weakened, so it is difficult to maintain the physical properties of the film. Especially in the heating step such as reflow in the processing step of the semiconductor device, it is easy to produce cracks and peeling due to degassing and shrinkage.

In order to suppress the peeling of the resin film from the Cu wiring during the reflow step, it is required to increase the glass transition point (Tg) and weight reduction temperature of the resin film. The hardening treatment is performed at the temperature, so the Tg becomes lower than the reflow temperature, resulting in the low-molecular compound remaining without volatilization. There is a tendency for Tg to increase by reducing the molecular weight between the cross-linking points of the cured film. However, if the negative photosensitive resin composition is increased, the concentration of the functional group or the functional group of the radical polymerizable compound generally used with the polyimide precursor is increased. The addition amount reduces the resolution of the relief pattern, so it is not easy to increase the Tg of the resin film while maintaining the resolution. In addition, in order to increase the thermal weight reduction temperature of the resin film, it is necessary to completely volatilize or immobilize the low-molecular compound in the resin film.

The present invention was conceived in view of such previous actual conditions, and one of its objects is to provide a surface with excellent storage stability and/or good adhesion with sealing materials such as mold resins, and when formed into multiple layers A negative photosensitive resin composition with good uniformity and crack resistance, and excellent elongation after the reliability test. In addition, an object of the present invention is to provide a method for forming a hardened relief pattern using the negative photosensitive resin composition of the present invention.

Yet another object of the present invention is to provide a photosensitive resin composition capable of producing a resin film with high Tg and thermal weight reduction temperature and excellent chemical resistance, or to improve the hardened relief pattern. The photosensitive resin composition with uniformity in the surface, the hardened embossed pattern and its manufacturing method. [Technical means to solve the problem]

{式中，X₁ 為4價有機基，Y₁ 為2價有機基，n₁ 為2～150之整數，R₁ 及R₂ 分別獨立為氫原子或1價有機基，並且R₁ 及R₂ 之至少一者為下述通式(2)所表示之1價有機基： [化2]

(式中，L₁ 、L₂ 及L₃ 分別獨立地為氫原子或碳數1～3之有機基，並且m₁ 為2～10之整數)}； (B)包含選自由胺基甲酸酯鍵、及脲鍵所組成之群中之至少1種的化合物； (C)光聚合起始劑；以及 (D)選自由3-甲氧基-N,N-二甲基丙醯胺、及3-丁氧基-N,N-二甲基丙醯胺所組成之群中之至少1種溶劑。 [2] 如項目1中記載之負型感光性樹脂組合物，其中上述(B)化合物為具有脲鍵之化合物。 [3] 如項目1或2中記載之負型感光性樹脂組合物，其中上述(B)化合物為下述通式(3)或(4)所表示之化合物： [化3]

{式中，R₇ 及R₈ 分別獨立地為可包含雜原子之碳數1～20之1價有機基，並且R₉ 及R₁₀ 分別獨立為氫原子、或可包含雜原子之碳數1～20之1價有機基} [化4]

{式中，R₁₁ 及R₁₂ 分別獨立地為可包含雜原子之碳數1～20之1價有機基，並且R₁₃ 為可包含雜原子之碳數1～20之2價有機基}。 [4] 如項目1至3中任一項記載之負型感光性樹脂組合物，其中上述(B)化合物包含選自由(甲基)丙烯醯基、羥基、及胺基所組成之群中之至少1種官能基。 [5] 如項目1至4中任一項記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物之通式(1)中之Y₁ 為下述通式(5)所表示之結構： [化5]

{式中，R₁₄ 及R₁₅ 分別獨立地為氫原子、或可包含鹵素原子之碳數1～10之1價有機基}。 [6] 如項目1至5中任一項記載之負型感光性樹脂組合物，其進而包含(E)防銹劑。 [7] 如項目6記載之負型感光性樹脂組合物，其中上述(E)防銹劑含有含氮雜環化合物。 [8] 如項目7記載之負型感光性樹脂組合物，其中上述含氮雜環化合物為唑類化合物。 [9] 如項目7記載之負型感光性樹脂組合物，其中上述含氮雜環化合物為嘌呤、或嘌呤衍生物。 [10] 如項目1至9中任一項記載之負型感光性樹脂組合物，其進而包含(F)矽烷偶合劑。 [11] 如項目1至10中任一項記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物之通式(1)中之X₁ 為包含選自由下述通式(20a)、(20b)、及(20c)所組成之群中之至少1種之結構， [化6]

{式中，R₆ 為選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之至少一者，並且l為選自0～2中之整數} [化7]

{式中，R₆ 分別獨立地為選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之至少一者，並且m分別獨立地為選自0～3中之整數} [化8]

{式中，R₆ 分別獨立地為選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之至少一者，並且m分別獨立地選自0～3中之整數}。 [12] 如項目1至11中任一項記載之負型感光性樹脂組合物，其包含： 上述(A)聚醯亞胺前驅物； 上述(B)化合物，其以上述(A)聚醯亞胺前驅物100質量份作為基準，為0.1～30質量份； 上述(C)光聚合起始劑，其以上述(A)聚醯亞胺前驅物100質量份作為基準，為0.1～20質量份； 上述(D)溶劑，其以上述(A)聚醯亞胺前驅物100質量份作為基準，為10～1000質量份。 [13] 一種負型感光性樹脂組合物，其包含： (A)具有下述通式(1)所表示之結構單元之聚醯亞胺前驅物： [化9]

{式中，X₁ 為4價有機基，Y₁ 為2價有機基，n₁ 為2～150之整數，R₁ 及R₂ 分別獨立為氫原子或1價有機基，並且R₁ 及R₂ 之至少一者為下述通式(2)所表示之1價有機基： [化10]

(式中，L₁ 、L₂ 及L₃ 分別獨立地為氫原子或碳數1～3之有機基，並且m₁ 為2～10之整數)}； (B)包含選自由胺基甲酸酯鍵、及脲鍵所組成之群中之至少1種的化合物； (C)光聚合起始劑；以及 (G)具有3個以上之聚合性官能基之聚合性不飽和單體。 [14] 一種負型感光性樹脂組合物，其包含 (A)具有下述通式(1)所表示之結構單元之聚醯亞胺前驅物： [化11]

{式中，X₁ 為4價有機基，Y₁ 為2價有機基，n₁ 為2～150之整數，R₁ 及R₂ 分別獨立為氫原子或1價有機基，並且R₁ 及R₂ 之至少一者為下述通式(2)所表示之1價有機基： [化12]

(式中，L₁ 、L₂ 及L₃ 分別獨立地為氫原子或碳數1～3之有機基，並且m₁ 為2～10之整數)}； (B)包含選自由胺基甲酸酯鍵、及脲鍵所組成之群中之至少1種的化合物； (C)光聚合起始劑；以及 (D1)溶劑，且 上述(A)聚醯亞胺前驅物之0.1 wt%N-甲基吡咯啶酮(NMP)溶液之i射線吸光度為0.03～0.3。 [15] 一種聚醯亞胺之製造方法，其包括：將如項目1至14中任一項記載之負型感光性樹脂組合物所包含之上述(A)聚醯亞胺前驅物轉化為聚醯亞胺的步驟。 [16] 一種硬化浮凸圖案之製造方法，其包括： (1)將如項目1至14中任一項記載之負型感光性樹脂組合物塗佈於基板上，於上述基板上形成感光性樹脂層之步驟； (2)對上述感光性樹脂層進行曝光之步驟； (3)對曝光後之上述感光性樹脂層進行顯影而形成浮凸圖案之步驟；及 (4)對上述浮凸圖案進行加熱處理而形成硬化浮凸圖案之步驟。 [17] 一種感光性樹脂組合物，其包含 (A1)聚醯亞胺前驅物、 (I)具有羥基及聚合性不飽和鍵之化合物、 (C1)感光劑、 (D2)溶劑、及 (J1)游離氯，且 以上述感光性樹脂組合物之總質量作為基準，上述游離氯之量為0.0001～2 ppm。 [18] 一種感光性樹脂組合物，其包含 (A1)聚醯亞胺前驅物、 (I)具有羥基及聚合性不飽和鍵之化合物、 (C1)感光劑、 (D2)溶劑、及 (J1)游離氯，且 將上述感光性樹脂組合物以硬化後之膜厚成為約10 μm之方式利用旋轉法塗佈於基盤上，利用加熱板以110℃加熱180秒而使上述感光性樹脂組合物硬化時，所獲得之塗膜中包含之上述游離氯之量以上述塗膜之總質量作為基準，為0.0001～5 ppm。 [19] 一種感光性樹脂組合物，其包含 (A1)聚醯亞胺前驅物、 (I)具有羥基及複數個聚合性不飽和鍵之化合物、 (C1)感光劑、 (D2)溶劑、及 (J1)游離氯及/或(J2)共價鍵結性氯，且 調整上述感光性樹脂組合物後，於23℃±0.5℃、相對濕度50%±10%下靜置了3天時之上述感光性樹脂組合物中的總氯量以上述感光性樹脂組合物之總質量作為基準，為0.0001～250 ppm。 [20] 一種感光性樹脂組合物，其包含 (A2)選自由聚醯亞胺及聚醯亞胺前驅物所組成之群中之至少1種以上之樹脂、 (C1)感光劑、及 (K)脲化合物，且 藉由以170℃對上述感光性樹脂組合物加熱2小時而使之硬化，使所得之硬化膜與溫度50℃、濃度2.38質量%之氫氧化四甲基銨五水合物(TMAH)之二甲基亞碸(DMSO)溶液接觸了10分鐘時， 接觸前與接觸後之上述硬化膜的以1500 cm^-1 之IR峰強度進行了標準化時的1778 cm^-1 附近之IR峰強度滿足下述式(1)： 0.1≦(接觸後峰強度/接觸前峰強度)≦0.8       (1)。 [21] 一種硬化膜，其中使硬化膜與溫度50℃、濃度2.38質量%之TMAH之DMSO溶液接觸了10分鐘時，接觸前與接觸後之上述硬化膜的以1500 cm^-1 之IR峰強度進行了標準化時的1778 cm^-1 附近之IR峰強度滿足下述式(1)： 0.1≦(接觸後峰強度/接觸前峰強度)≦0.8       (1)。 [發明之效果]The inventors of the present invention found that by combining a specific polyimide precursor, a compound containing a specific bond, a photopolymerization initiator, and a specific solvent or polymerizable unsaturated monomer; A resin composition containing a compound with a sexually unsaturated bond, and a free chlorine and/or covalently bonded chlorine adjusted to a specific amount; and/or the cured film of a photosensitive resin composition containing a urea compound is exposed to specific conditions When contacting with the DMSO solution of TMAH, the intensity ratio of the IR peak of the cured film before and after the contact falls within a specific range to solve the above-mentioned problems, thereby completing the present invention. Examples of embodiments of the present invention are listed below. [1] A negative photosensitive resin composition comprising: (A) a polyimide precursor having a structural unit represented by the following general formula (1): [化1]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ and R ₂ is at least one of the following general formula (2) as the monovalent organic group represented by: [Chemical formula 2]

(In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group with a carbon number of 1 to 3, and m ₁ is an integer of 2 to 10)}; (B) includes selected from amino formic acid At least one compound from the group consisting of an ester bond and a urea bond; (C) a photopolymerization initiator; and (D) selected from 3-methoxy-N,N-dimethylpropanamide, And at least one solvent in the group consisting of 3-butoxy-N,N-dimethylpropanamide. [2] The negative photosensitive resin composition as described in item 1, wherein the compound (B) is a compound having a urea bond. [3] The negative photosensitive resin composition as described in item 1 or 2, wherein the compound (B) is a compound represented by the following general formula (3) or (4): [化3]

{In the formula, R ₇ and R ₈ are each independently a monovalent organic group with 1 to 20 carbon atoms that may contain a hetero atom, and R ₉ and R ₁₀ are each independently a hydrogen atom or a carbon number that may contain a hetero atom 1 ~20 monovalent organic groups} [Chemical 4]

{In the formula, R ₁₁ and R ₁₂ are each independently a monovalent organic group with _{1 to 20 carbons that may contain a hetero atom, and R 13} is a divalent organic group with 1 to 20 carbons that may contain a hetero atom}. [4] The negative photosensitive resin composition according to any one of items 1 to 3, wherein the compound (B) includes a group selected from the group consisting of (meth)acrylic groups, hydroxyl groups, and amino groups At least one functional group. [5] The negative photosensitive resin composition according to any one of items 1 to 4, wherein Y ₁ in the general formula (1) of the polyimide precursor (A) is the following general formula (5) The structure represented by ): [化5]

{In the formula, R ₁₄ and R ₁₅ are each independently a hydrogen atom, or a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom}. [6] The negative photosensitive resin composition according to any one of items 1 to 5, which further contains (E) a rust inhibitor. [7] The negative photosensitive resin composition according to item 6, wherein the (E) rust inhibitor contains a nitrogen-containing heterocyclic compound. [8] The negative photosensitive resin composition according to item 7, wherein the nitrogen-containing heterocyclic compound is an azole compound. [9] The negative photosensitive resin composition according to item 7, wherein the nitrogen-containing heterocyclic compound is a purine or a purine derivative. [10] The negative photosensitive resin composition according to any one of items 1 to 9, which further contains (F) a silane coupling agent. [11] The negative photosensitive resin composition according to any one of items 1 to 10, wherein X ₁ in the general formula (1) of the (A) polyimide precursor is selected from the group consisting of: The structure of at least one of the group consisting of formulas (20a), (20b), and (20c), [化6]

{In the formula, R ₆ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and l is selected from 0 to Integer in 2} [to 7]

{In the formula, R _{6 is} each independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorinated hydrocarbon group with 1 to 10 carbons, and m is each independently Ground is an integer selected from 0～3} [化8]

{In the formula, R _{6 is} each independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorinated hydrocarbon group with 1 to 10 carbons, and m is each independently Ground is selected from an integer of 0 to 3}. [12] The negative photosensitive resin composition according to any one of items 1 to 11, which comprises: the above-mentioned (A) polyimide precursor; the above-mentioned (B) compound, which is based on the above-mentioned (A) polyimide 100 parts by mass of the imine precursor as a reference, 0.1-30 parts by mass; the above (C) photopolymerization initiator, which is 0.1-20 parts by mass based on 100 parts by mass of the polyimine precursor of the above (A) Parts; The (D) solvent is 10 to 1000 parts by mass based on 100 parts by mass of the (A) polyimide precursor. [13] A negative photosensitive resin composition comprising: (A) a polyimide precursor having a structural unit represented by the following general formula (1): [化9]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ and R ₂ is at least one of the following general formula (2) as the monovalent organic group represented by: [formula 10]

(In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group with a carbon number of 1 to 3, and m ₁ is an integer of 2 to 10)}; (B) includes selected from amino formic acid At least one compound from the group consisting of an ester bond and a urea bond; (C) a photopolymerization initiator; and (G) a polymerizable unsaturated monomer having 3 or more polymerizable functional groups. [14] A negative photosensitive resin composition comprising (A) a polyimide precursor having a structural unit represented by the following general formula (1): [化11]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ and R ₂ is at least one of the following general formula (2) as the monovalent organic group represented by: [formula 12]

(In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group with a carbon number of 1 to 3, and m ₁ is an integer of 2 to 10)}; (B) includes selected from amino formic acid At least one compound in the group consisting of an ester bond and a urea bond; (C) a photopolymerization initiator; and (D1) a solvent, and the above-mentioned (A) polyimide precursor 0.1 wt% N- The i-ray absorbance of the methylpyrrolidone (NMP) solution is 0.03-0.3. [15] A method for producing polyimide, comprising: converting the (A) polyimide precursor contained in the negative photosensitive resin composition as described in any one of items 1 to 14 into polyimide The step of imine. [16] A method of manufacturing a hardened relief pattern, comprising: (1) applying the negative photosensitive resin composition as described in any one of items 1 to 14 on a substrate, and forming photosensitive on the substrate The step of the resin layer; (2) the step of exposing the photosensitive resin layer; (3) the step of developing the photosensitive resin layer after the exposure to form a relief pattern; and (4) the step of exposing the relief pattern A step of heat treatment to form a hardened relief pattern. [17] A photosensitive resin composition comprising (A1) a polyimide precursor, (I) a compound having a hydroxyl group and a polymerizable unsaturated bond, (C1) a photosensitizer, (D2) a solvent, and (J1) ) Free chlorine, and based on the total mass of the photosensitive resin composition, the amount of the free chlorine is 0.0001 to 2 ppm. [18] A photosensitive resin composition comprising (A1) a polyimide precursor, (I) a compound having a hydroxyl group and a polymerizable unsaturated bond, (C1) a photosensitizer, (D2) a solvent, and (J1) ) Free chlorine, and apply the photosensitive resin composition to the base plate by a spin method so that the film thickness after curing becomes about 10 μm, and heat it at 110°C for 180 seconds on a hot plate to make the photosensitive resin composition During curing, the amount of free chlorine contained in the obtained coating film is 0.0001 to 5 ppm based on the total mass of the coating film. [19] A photosensitive resin composition comprising (A1) a polyimide precursor, (I) a compound having a hydroxyl group and a plurality of polymerizable unsaturated bonds, (C1) a photosensitizer, (D2) a solvent, and (J1) Free chlorine and/or (J2) covalently bonded chlorine, and after adjusting the photosensitive resin composition, it is left standing at 23℃±0.5℃, relative humidity 50%±10% for 3 days The total amount of chlorine in the photosensitive resin composition is 0.0001 to 250 ppm based on the total mass of the photosensitive resin composition. [20] A photosensitive resin composition comprising (A2) at least one resin selected from the group consisting of polyimine and polyimide precursors, (C1) sensitizer, and (K ) A urea compound, and the photosensitive resin composition is cured by heating the photosensitive resin composition at 170°C for 2 hours, and the resulting cured film is cured with tetramethylammonium hydroxide pentahydrate at a temperature of 50°C and a concentration of 2.38% by mass ( when TMAH) of dimethyl sulfoxide (DMSO) was contacted for 10 minutes, prior to contact with the curing of the film after the contact was 1778 cm IR ^{cm -1} peak in the IR at the normalized peak intensity of 1500 cm ^-1 The intensity satisfies the following formula (1): 0.1≦(peak intensity after contact/peak intensity before contact)≦0.8 (1). [21] A cured film in which when the cured film is in contact with a DMSO solution of TMAH at a temperature of 50°C and a concentration of 2.38% by mass for 10 minutes, the IR peak intensity ^{of the cured film before and after the contact is 1500 cm -1} The normalized ^{IR peak intensity around 1778 cm -1} satisfies the following formula (1): 0.1≦(peak intensity after contact/peak intensity before contact)≦0.8 (1). [Effects of Invention]

According to the present invention, it is possible to provide a product with excellent adhesion to a sealing material and storage stability, excellent in-plane uniformity when formed into multiple layers, suppression of cracks, etc., and excellent elongation in a reliability test. A type photosensitive resin composition can also provide a method for forming a hardened relief pattern using the negative type photosensitive resin composition. Furthermore, according to the present invention, it is possible to provide a negative photosensitive resin composition used in fan-out semiconductor packages that has good adhesion to the mold resin.

According to the present invention, it is possible to provide a photosensitive resin composition capable of producing a resin film with a high glass transition temperature and a high thermal weight reduction temperature and excellent chemical resistance while maintaining the resolution of the formed relief pattern. In one embodiment, after the embossed pattern is formed, the crosslinking density of the polymer in the resin can be increased, and the glass transition temperature of the cured film tends to be higher while the resolution is maintained. Moreover, in one embodiment, the low boiling point compound in the membrane can be immobilized by reaction, so that the thermal weight reduction temperature can be increased. In another embodiment, by setting the crosslink density and free chlorine to a specific amount, the penetration of the drug solution into the cured film can be prevented, and therefore the chemical resistance of the embossed pattern can also be improved.

According to the present invention, it is possible to provide a photosensitive resin composition that can improve the in-plane uniformity of the cured relief pattern when two or more layers of the cured relief pattern of the photosensitive resin composition are laminated, the cured relief pattern, and a manufacturing method thereof.

Hereinafter, a mode for implementing the present invention (hereinafter also referred to as "this embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist. In addition, throughout this specification, when there are plural structures in the molecule represented by the same symbol in the general formula, unless otherwise specified, they are independently selected and may be the same or different from each other. In addition, in this specification, "negative type" refers to a photosensitive resin composition that dissolves in the unexposed part and remains in the exposed part during development.

<Negative photosensitive resin composition> (First aspect) The negative photosensitive resin composition of the first aspect of the present invention includes: (A) a specific polyimide precursor, and (B) includes selected from the group consisting of urethane bond and urea bond At least one compound, (C) a photopolymerization initiator, and (D) are selected from 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N- At least one solvent in the group consisting of dimethyl acetamide.

From the viewpoints of easily obtaining the effects of the present invention and obtaining higher chemical resistance, the negative photosensitive resin composition preferably contains: (A) a polyimide precursor; (B) a compound, which (A) 100 parts by mass of the polyimide precursor as a reference, which is 0.1-30 parts by mass; (C) a photopolymerization initiator, which is based on 100 parts by mass of the (A) polyimine precursor as a reference, which is 0.1-20 parts by mass; and (D) the solvent, which is 10-1000 parts by mass based on 100 parts by mass of the (A) polyimide precursor.

(2nd aspect) The negative photosensitive resin composition of the second aspect of the present invention includes: (A) a polyimide precursor; (B) includes at least one selected from the group consisting of a urethane bond and a urea bond One type of compound; (C) a photopolymerization initiator; and (G) a polymerizable unsaturated monomer having 3 or more polymerizable functional groups.

From the viewpoint of obtaining higher chemical resistance, the negative photosensitive resin composition preferably contains: (A) a polyimide precursor; (B) a compound, which is based on (A) polyimide 100 parts by mass of the precursor as a reference, 0.1-30 parts by mass; (C) photopolymerization initiator, which is 0.1-20 parts by mass based on 100 parts by mass of the polyimide precursor of (A); (G ) A polymerizable unsaturated monomer having 3 or more polymerizable functional groups, which is 1-50 parts by mass based on 100 parts by mass of the (A) polyimide precursor. Thereby, it is easy to exert the effect of the present invention.

(3rd aspect) The third aspect of the negative photosensitive resin composition of the present invention includes: (A) a specific polyimide precursor; (B) includes selected from the group consisting of urethane bond and urea bond At least one compound (hereinafter, also referred to as "urethane/urea compound"); (C) photopolymerization initiator; and (D1) solvent, and the above (A) polyimide precursor The i-ray absorbance of 0.1 wt% N-methylpyrrolidone (NMP) solution is 0.03～0.3.

From the viewpoints of easily obtaining the effects of the present invention and obtaining higher chemical resistance, the negative photosensitive resin composition preferably contains: (A) a polyimide precursor; (B) a compound, which (A) 100 parts by mass of the polyimide precursor as a reference, which is 0.1-30 parts by mass; (C) a photopolymerization initiator, which is based on 100 parts by mass of the (A) polyimine precursor as a reference, which is 0.1-20 parts by mass; and (D1) solvent, which is 10-1000 parts by mass based on 100 parts by mass of the (A) polyimide precursor.

<Photosensitive resin composition> (4th aspect) The photosensitive resin composition of the fourth aspect of the present invention includes: (A1) a polyimide precursor; (I) a compound having a hydroxyl group and a polymerizable unsaturated bond; (C1) a photosensitizer; (D2) a solvent; And a specific amount of (J1) free chlorine and/or (J2) covalently bonded chlorine. The photosensitive resin composition contains other components as needed.

The photosensitive resin composition of the fourth aspect may be a negative type or a positive type depending on the desired use. From the viewpoint of the physical properties of the polyimide precursor (A1) below, the negative type is preferred.

It is possible to introduce a compound having a structure similar to that of an imidation accelerator (basic compound) into the side chain of the polymer of the fourth aspect, thereby obtaining a higher level than the case of using an imidation accelerator as an additive It is possible to obtain a photosensitive resin composition that has both storage stability and chemical resistance.

For the photosensitive resin composition of the fourth aspect, it is preferable that when the resin composition is stored at a temperature of 23° C. and a humidity of 50% Rh for 4 weeks, the viscosity change rate of the resin composition is within 5% compared with the initial stage. . Furthermore, the photosensitive resin composition is preferably such that when the resin composition is heated at 170°C for 2 hours to obtain a cured coating film, the imidization rate of the cured coating film is 70% or more. The imidization rate is more preferably 85% or more. In this way, in one embodiment, the photosensitive resin composition can provide a polyimide with a high imidization rate and excellent storage stability and chemical resistance.

(Fifth aspect) The photosensitive resin composition of the fifth aspect of the present invention includes: (A2) At least one resin selected from the group consisting of polyimine and polyimide precursors, (C1) Sensitizer, and (K) Urea compounds.

The photosensitive resin composition of the fifth aspect can be heated at 170°C for 2 hours to obtain a cured film. The cured film was brought into contact with a dimethyl sulfide (DMSO) solution of tetramethylammonium hydroxide pentahydrate (TMAH) at a temperature of 50°C and a concentration of 2.38% by mass (hereinafter, also referred to as "standard TMAH solution") ^{At 10 minutes, the IR peak intensity around 1778 cm -1} when normalized by the IR peak intensity of ^{1500 cm -1} of the cured film before and after the contact satisfies the following formula (1). 0.1≦(peak intensity after contact/peak intensity before contact)≦0.8 (1)

When the IR peak intensity of the cured film is within the above range, the hydrophilicity of the cured film is increased, and the cured film has wettability suitable for further coating the photosensitive resin composition on the cured film. From the viewpoint of chemical resistance, the value of peak intensity after contact/peak intensity before contact is preferably 0.1 or more, more preferably 0.3 or more, and still more preferably 0.5 or more. The cured film whose peak strength after contact/peak strength before contact is less than 0.1 lacks chemical resistance. From the viewpoint of wettability, the value of peak intensity after contact/peak intensity before contact is preferably 0.8 or less, more preferably 0.7 or less, and still more preferably 0.6 or less.

The temperature, concentration, and contact conditions of the above standard TMAH solution are used to determine the peak intensity after contact/peak intensity before contact of the photosensitive resin composition. Please note that the use of the photosensitive resin composition in the fifth aspect is not limited Method or use. In the photosensitive resin composition of the fifth aspect, the (K) urea compound is further combined with the component (A2) and the component (C1), so that the peak intensity after contact/the peak intensity before contact can be adjusted to the above formula (1) Trends within the range.

The change in the film thickness of the standard TMAH solution before and after the contact is preferably from 1 nm to 1000 nm. If the solubility of the hardened embossed pattern in the alkaline solution is low, the pattern deterioration (cracking, pattern shape collapse) can be effectively suppressed, so the film thickness of the hardened film before and after contact with the standard TMAH solution The amount of change is more preferably 600 nm or less, and still more preferably 300 nm or less. The amount of change in the film thickness of the cured film is measured by adjusting the film thickness of the cured film before contact to about 3 μm.

In the cured film before contact with the standard TMAH solution, from the viewpoint of degassing or curing shrinkage in the step in the case of forming a multilayer body, the imidization rate is preferably 70% or more and 100% or less. When the imidization rate is more than 70%, the degassing property or hardening shrinkage can be suppressed in the step after contact with the alkaline solution. The imidization rate is more preferably 80% or more, and still more preferably 90% or more.

＜Ingredients＞ The components of the resin composition of the first to fifth aspects, the common constituent elements of the first to fifth aspects, and preferred embodiments are described below.

{式中，X₁ 為4價有機基，Y₁ 為2價有機基，n₁ 為2～150之整數，R₁ 及R₂ 分別獨立為氫原子或1價有機基，並且R₁ 及R₂ 之至少一者為下述通式(2)所表示之1價有機基}(A, A1) Polyimide precursor The fourth and fifth aspect of (A1) Polyimine precursor system photosensitive resin composition contains the resin component, preferably having the same as the first to the first to the first The three types of (A) polyimide precursors have the same structural unit. (A) The polyimide precursor is a resin component contained in the negative photosensitive resin composition, and is converted into polyimide by performing a heat cyclization treatment. (A) The polyimide precursor is a polyimide having a structural unit represented by the following general formula (1). [化13]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ and R ₂ is at least one of the following general formula (2) represents a monovalent organic group of 1}

In one embodiment, when the N-methylpyrrolidone solution containing 0.1 wt% of the polyimide precursor of (A) is adjusted, the i-ray absorbance of the adjusted N-methylpyrrolidone solution can be 0.03 ~ 0.3 value. In addition, the i-ray absorbance can be measured by the method described in the following Examples.

{式中，L₁ 、L₂ 及L₃ 分別獨立地為氫原子或碳數1～3之1價有機基，並且m₁ 為2～10之整數}In the general formula (1), it is preferable that R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, _{and at least one of R 1} and R ₂ is the following general formula ( 2) The indicated monovalent organic group. [化14]

{In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group with 1 to 3 carbons, and m ₁ is an integer of 2 to 10}

In one embodiment, from the viewpoint of high resolution, (A) the monovalent organic group represented by the general formula (2) contained in the polyimide precursor is relative to the monovalent organic group represented by the general formula (1) The ratio of all R ₁ and R ₂ of the precursor is preferably 50 mol% to 100 mol%, and further, from the viewpoint of high chemical resistance and sensitivity, it is more preferably 75 mol% to 100 mol% %.

_{In another embodiment, with regard to the ratio of R 1} and R ₂ in the general formula (1) that are hydrogen atoms, based on _{the molar number of R 1} and R ₂ as a whole, it is preferably 10% or less, more preferably 5% or less, more preferably 1% or less. In addition, the ratio of R ₁ and R ₂ in the general formula (1) to the monovalent organic group represented by the general formula (2) is preferably 70 based on the molar number of _{R 1} and R _{2 as a whole} % Or more, more preferably 80% or more, and still more preferably 90% or more. From the viewpoint of photosensitive characteristics and storage stability, it is preferable that the ratio of hydrogen atoms and the ratio of organic groups of the general formula (2) be within the above-mentioned range.

{式中，R6為選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之至少一者，l為選自0～2中之整數，m為選自0～3中之整數，並且n為選自0～4中之整數}In general formula (1), n _{1 should} just be an integer of 2 to 150. From the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, it is preferably an integer of 3 to 100, and more preferably 5 to An integer of 70. In the general formula (1), _{the tetravalent organic group represented by X 1} is preferably an organic group having 6 to 40 carbon atoms, more preferably -COOR ₁ group and -COOR, from the viewpoint of both heat resistance and photosensitive characteristics _{An aromatic group or an alicyclic aliphatic group in which the 2} group and the -CONH- group are in the ortho position to each other. Specific examples of the tetravalent organic group represented by X ₁ include an aromatic ring-containing organic group having 6 to 40 carbon atoms, for example, a group having a structure represented by the following general formula (20). [化15]

{In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and l is selected from 0 to 2 M is an integer selected from 0 to 3, and n is an integer selected from 0 to 4}

{式中，R6分別獨立地為選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之至少一者，並且l為選自0～2中之整數} [化17]

{式中，R6分別獨立地為選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之至少一者，並且m分別獨立地為選自0～3中之整數} [化18]

{式中，R6分別獨立地為選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之至少一者，並且m分別獨立地為選自0～3中之整數}The structure of X ₁ may be one type or a combination of two or more types. From the viewpoint of both heat resistance and photosensitive characteristics, it is particularly preferable to have an _{X 1 group having a structure represented by the above formula (20).} As the X ₁ group, the above formula ( 20) A structure represented by at least one of the following formulas (20a), (20b), and (20c) among the structures shown. [化16]

{In the formula, R6 is each independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and l is selected from Integer in 0～2} [化17]

{In the formula, R6 is each independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and m is each independently Is an integer selected from 0～3} [化18]

{In the formula, R6 is each independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and m is each independently Is an integer selected from 0～3}

{式中，R6分別獨立地為選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之至少一者，並且n為選自0～4中之整數}In the above general formula (1), _{the divalent organic group represented by Y 1} is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a carbon number of 6 to, from the viewpoint of achieving both heat resistance and photosensitive characteristics. The aromatic group of 40 includes, for example, a structure represented by the following formula (21). [化19]

{In the formula, R6 is each independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorinated hydrocarbon group with 1 to 10 carbons, and n is selected from Integer in 0～4}

The structure of Y ₁ can be one type or a combination of two or more types. From the viewpoint of both heat resistance and photosensitive characteristics, it is particularly preferable to have a _{Y 1 group having a structure represented by the above formula (21).}

。In one embodiment, as the Y ₁ group, in terms of the rate of imidization, outgassing, copper adhesion, and chemical resistance during low-temperature heating, in the structure represented by the above formula (21) Especially the structure represented by the following formula is better: [化20]

.

{式中，R6為選自由氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，並且n為選自0～4中之整數}。In another embodiment, as the Y ₁ group, in terms of the imidization rate, outgassing, copper adhesion, and chemical resistance during low-temperature heating, the structure represented by the above formula (21) Especially the structure represented by the following formula is better: [化21]

{In the formula, R6 is a _{monovalent group selected from the group consisting of fluorine atoms, C 1} to C ₁₀ hydrocarbon groups, and C ₁ to C ₁₀ fluorinated hydrocarbon groups, and n is an integer selected from 0 to 4 }.

{式中，R₁₄ 及R₁₅ 分別獨立地為氫原子、或可包含鹵素原子之碳數1～10之1價有機基} 其等之中，就硬化膜之玻璃轉移溫度(Tg)或楊氏模數之觀點而言，R₁₄ 及R₁₅ 之至少一者或兩者較佳為甲基或三氟甲基。The Y ₁ group is particularly preferably a structure represented by the following formula (5) from the viewpoint of chemical resistance, in-plane uniformity when formed into multiple layers, or suppression of cracks. [化22]

{In the formula, R ₁₄ and R ₁₅ are each independently a hydrogen atom, or a monovalent organic group with 1 to 10 carbons that may contain a halogen atom} Among them, the glass transition temperature (Tg) of the cured film or Yang From the viewpoint of modulus, at least one or both of _{R 14} and R _{15 are preferably methyl or trifluoromethyl.}

In addition, as the Y ₁ group, from the viewpoint of ease of controlling the absorbance of i-rays, in-plane uniformity in the case of being formed in multiple layers, or suppression of cracks, the structure represented by the following formula (5a) is particularly preferable . [化23]

In the structure represented by the formula (5a), the positions of the benzene ring and the connection part of the NH in the general formula (1) are respectively independent, relative to -O-, it may be 2-position, 3-position, or 4 bit. From the viewpoint of easily obtaining the effects of the present invention, in the structure represented by formula (5a), the position of the connecting portion between the benzene ring and the NH in the general formula (1) is preferably the 4-position relative to -O- .

_{L 1} in the above general formula (2) is preferably a hydrogen atom or a methyl group, and from the viewpoint of photosensitive properties, L ₂ and L _{3 are} preferably a hydrogen atom. Furthermore, in the general formula (2), m ₁ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitivity.

{式中，R₁ 、R₂ 、及n₁ 係上述通式(1)中所定義者}。In one embodiment, the (A, A1) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (8): [化24]

{In the formula, R ₁ , R ₂ , and n ₁ are those defined in the above general formula (1)}.

In the general formula (8), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (2). By making the (A, A1) polyimine precursor contain the polyimine precursor having the structural unit represented by the general formula (8), it is possible to obtain the polyimine precursor containing the above formula (5) or (5a) In addition to the effects (for example, improved crack resistance when formed into multiple layers), in addition to this, the effects of especially resolution are increased, and/or resolution, imidization rate, and chemical resistance It becomes better, especially the in-plane uniformity becomes better.

{式中，R₁ 、R₂ 、及n₁ 係上述通式(1)中所定義者}。In one embodiment, from the viewpoint of the effect brought by the inclusion of the above formula (5) and/or the resolution, the (A, A1) polyimide precursor also preferably has the following general formula (9) The polyimide precursor of the structural unit: [化25]

{In the formula, R ₁ , R ₂ , and n ₁ are those defined in the above general formula (1)}.

In the general formula (9), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (2).

{式中，R₁ 、R₂ 、及n₁ 係上述中所定義者}。In one embodiment, (A, A1) the polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (9A): [化26]

{Where, R ₁ , R ₂ , and n ₁ are those defined above}.

In the general formula (9A), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the above general formula (2).

{式中，R₁ 、R₂ 、及n₁ 係上述通式(1)中所定義者}In one embodiment, from the viewpoint of the effect brought by the inclusion of the above formula (5) and the resolution, the (A, A1) polyimide precursor also preferably has the following general formula (9B) The polyimide precursor of the structural unit shown. [化27]

{Where, R ₁ , R ₂ , and n ₁ are those defined in the above general formula (1)}

In the general formula (9B), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the above general formula (2).

In general formulas (8), (9) and (9B), R ₁ , R ₂ , and n _{1 in one} formula may be the same as or different from _{R 1} , R ₂ , and n ₁ in the remaining formulas, respectively.

{式中，R₁ 、R₂ 、及n₁ 係上述中所定義者}。In one embodiment, especially from the viewpoint of chemical resistance, the (A, A1) polyimide precursor preferably includes a polyimide having a structural unit represented by the following general formula (9C) Amine precursor: [化28]

{Where, R ₁ , R ₂ , and n ₁ are those defined above}.

In the general formula (9C), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the above general formula (2).

{式中，R₁ 、R₂ 、及n₁ 係上述中所定義者}。In one embodiment, especially from the viewpoint of chemical resistance, the (A, A1) polyimide precursor preferably includes a polyimide having a structural unit represented by the following general formula (9D) Amine precursor: [化29]

{Where, R ₁ , R ₂ , and n ₁ are those defined above}.

In the general formula (9D), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (2).

In one embodiment, the (A, A1) polyimide precursor contains both the structural unit represented by the general formula (9C) and the structural unit represented by the general formula (9D), especially the solution The trend toward higher image quality. For example, the (A, A1) polyimide precursor may include a copolymer of the structural unit represented by the general formula (9C) and the structural unit represented by the general formula (9D), or it may also be the general formula (9C) A mixture of the polyimide precursor represented by the formula (9D).

In another embodiment, the (A, A1) polyimide precursor includes both the structural unit represented by the general formula (9C) and the structural unit represented by the general formula (9A), especially There is a tendency for the resolution to become higher. For example, the (A, A1) polyimide precursor may include a copolymer of the structural unit represented by the general formula (9C) and the structural unit represented by the general formula (9A), or it may also be the general formula (9C) A mixture of the polyimine precursor represented by the formula (9A).

The i-ray absorbance of the 0.1 wt% N-methylpyrrolidone solution of (A) polyimide precursor of the third aspect is 0.03 to 0.3, and from the viewpoint of developability, it is preferably 0.05 or more, It is more preferably 0.07 or more, and particularly preferably 0.09 or more. (A) The i-ray absorbance of the 0.1 wt% N-methylpyrrolidone solution of the polyimide precursor of one embodiment is preferably 0.28 or less from the viewpoint of the adhesion between the sealing material and the redistribution layer, It is more preferably 0.25 or less, and particularly preferably 0.22 or less.

By making the i-ray absorbance of the 0.1 wt% NMP solution of the polyimide precursor (A) of the third aspect within the above range, the adhesion to the sealant is excellent, and it is not clear that the resin is the first layer Whether or not cracking can be suppressed when the second layer film is formed from the resin composition of the present embodiment on the film, the inventors of the present invention consider as follows.

It is believed that the polyimide or polyimine precursor will be colored due to the interaction between the polymers, and the higher i-ray absorbance means that the interaction between the polymers is stronger. Here, the present inventors believe that the (B) urethane/urea compound of the present embodiment exists in the vicinity of the polyimide precursor and promotes the imidization, thereby being easily converted into polyimide , Can inhibit cracking. It is believed that when the absorbance of the polyimide precursor is significantly higher, the interaction between the polyimide precursors is stronger than (B) the interaction between the urethane/urea compound and the polyimide precursor , Therefore (B) the urethane/urea compound will not work efficiently. On the other hand, it is considered that when the i-ray absorbance of the polyimide precursor is significantly lower (that is, when the polyimide precursor itself has fewer interacting parts), (B) urethane The ester/urea compound does not sufficiently interact with the polyimide precursor, so (B) the urethane/urea compound aggregates each other, and (B) the urethane/urea compound and the polyimide precursor Things are not functioning efficiently. Therefore, the effect of the present invention can be obtained when the i-ray absorbance of the polyimide precursor is adjusted appropriately so that the i-ray absorbance is within the above-mentioned numerical range.

In order to control the i-ray absorbance of the 0.1 wt% N-methylpyrrolidone solution of the (A) polyimine precursor of this embodiment within the above range, the intermolecular of the polyimine precursor can be controlled Interaction to implement. For example, when the i-ray absorbance is controlled to a low value, it is preferable to select the following acid dianhydrides that contain heteroatoms and have a larger free volume selected from 4,4'-oxydiphthalic dianhydride, And at least one of the group consisting of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride. In the case of controlling the i-ray absorbance to a higher value, it is preferable to select the following acid dianhydrides, which are more likely to cause intermolecular interactions, to be selected from pyromellitic dianhydride (PMDA) and diphenyl ether-3, At least one of the group consisting of 3',4,4'-tetracarboxylic dianhydride. In addition, when the i-ray absorbance is controlled to a low value, it is preferable to select the following diamine compounds that contain heteroatoms and have a large free volume selected from 4,4-diaminodiphenyl ether and 4 ,4'-Diamino-2,2'-bis(trifluoromethyl)-biphenyl group consisting of at least one species. In the case of controlling the absorbance of i-rays to a higher value, it is preferable to select from the group consisting of p-phenylenediamine, m-phenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, And at least one of the group consisting of 2,2'-dimethyl-4,4'-diaminobiphenyl.

In order to control the i-ray absorbance within the above range, the above-mentioned acid dianhydride (an acid anhydride that is preferable for controlling the i-ray absorbance to a higher value and/or an acid anhydride that is preferred for controlling the i-ray absorbance to a lower value) ), and the above-mentioned diamines (diamines that are better for controlling i-ray absorbance to a higher value, and/or diamines that are better for controlling i-ray absorbance to a lower value) can be used to make poly The raw material of the imine precursor can also be blended into the obtained polyimide precursor.

In addition, when the molecular weight of the (A) polyimide precursor of the present embodiment is measured by gel permeation chromatography in terms of polystyrene conversion weight average molecular weight, it is preferably 8,000 to 150,000, more preferably 9,000～50,000. When the weight average molecular weight is more than 8,000, the mechanical properties are good. When the weight average molecular weight is less than 150,000, the dispersion in the developer is good, and the resolution of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to choose from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

The degree of dispersion represented by the weight average molecular weight (Mw)/number average molecular weight (Mn) of the (A) polyimide precursor of this embodiment (sometimes also referred to as "molecular weight distribution") is preferably controlled at 2.1 to 2.8. By controlling the degree of dispersion to 2.1 or more, (B) the urea/urethane compound further exerts an effect on crack suppression and adhesion. By controlling the dispersion degree to 2.8 or less, the developability tends to be good. The degree of dispersion is more preferably 2.1 to 2.5, and still more preferably 2.2 to 2.4.

Regarding the degree of dispersion of the (A) polyimide precursor of an embodiment, for example, in the following purification step of the polyimide precursor, it can be changed by using a poor solvent to analyze the polymer composition. The amount of poor solvent is controlled. Generally speaking, low-molecular compounds dissolve in poor solvents. Therefore, if the amount of poor solvent is increased, the degree of dispersion becomes relatively small. On the other hand, if the amount of poor solvent is decreased, the degree of dispersion tends to increase. Therefore, the degree of dispersion can be controlled by adjusting the amount of poor solvent. Furthermore, in another embodiment, it is also possible to obtain a polyimide precursor with a greater degree of dispersion by mixing a plurality of polyimide precursors with different degrees of dispersion with each other.

When there are two or more kinds of polymers contained in the photosensitive resin composition, the i-ray absorbance can be measured for the mixed polymer mixed in each mass ratio. Therefore, when two or more types of polymers are used in this embodiment, any one of the following (1-1) to (1-3) may be included. (1-1) The following mixed polymer is used, and the mixed polymer uses two or more polymers whose i-ray absorbance falls within the above-mentioned range; (1-2) The following mixed polymer is used, the mixed polymer is prepared by combining the above-mentioned i-ray absorbance with at least one polymer within the above-mentioned range and the above-mentioned i-ray absorbance with at least one polymer outside the above-mentioned range The polymers are used together in a prescribed mass ratio, and the above-mentioned i-ray absorbance is controlled within the above-mentioned range; (1-3) The following mixed polymer is used. The mixed polymer uses two or more polymers whose i-ray absorbance is outside the above-mentioned range in a predetermined mass ratio to control the i-ray absorbance at Within the above range.

When the photosensitive resin composition contains two or more polymers, the mass average molecular weight (Mw) and number average molecular weight (Mn) can be measured and calculated for the mixed polymer mixed in each mass ratio Degree of dispersion. Therefore, when two or more types of polymers are used in this embodiment, any one of the following (2-1) to (2-3) may be included. (2-1) The following mixed polymer is used, and the mixed polymer uses two or more polymers with the above-mentioned dispersion degree in the above-mentioned range; (2-2) The following mixed polymer is used, the mixed polymer is made by combining the above-mentioned dispersion degree of one or more polymers within the above-mentioned range and the above-mentioned dispersion degree outside the above-mentioned range of one or more polymers Use the specified mass ratio together, and control the above-mentioned dispersion within the above-mentioned range; (2-3) The following mixed polymer is used. The mixed polymer controls the above-mentioned degree of dispersion in the above-mentioned range by combining two or more polymers whose above-mentioned degree of dispersion is outside the above-mentioned range in a predetermined mass ratio. Inside.

(A2) At least one resin selected from the group consisting of polyimine and polyimide precursors The photosensitive resin composition may contain at least one resin selected from the group consisting of polyimine and polyimide precursors as the (A2) component. The polyimide precursor as the component (A2) may be the (A, A1) polyimide precursor described above. The polyimide as the component (A2) is not particularly limited, and it can be obtained by heating and cyclizing the polyimide precursor. As the (A2) component, a mixture of polyimine and polyimine precursor can be used.

(A, A1) Preparation of polyimide precursor (A, A1) by the precursor of polyimide is obtained as follows: first, the above-containing tetravalent organic group of X ₁ tetracarboxylic dianhydride, After reacting with alcohols having photopolymerizable unsaturated double bonds and any alcohols not having unsaturated double bonds to prepare partially esterified tetracarboxylic acid (hereinafter also referred to as acid/ester body), It undergoes amide polycondensation with the above-mentioned diamines containing the divalent organic group Y _1.

(Preparation of acid/ester body) In this embodiment, the _{tetracarboxylic dianhydride containing the tetravalent organic group X 1} as a precursor suitable for preparing (A) polyimide is represented by the above general formula (20) The tetracarboxylic dianhydride shown is representative, for example, pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3 ,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, Diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3, 4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(hexa Fluoroisopropylidene) diphthalic anhydride and the like. Preferably, examples include: pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4' -Tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride. Moreover, these etc. can be used individually or in mixture of 2 or more types.

In this embodiment, as alcohols with photopolymerizable unsaturated double bonds that can be preferably used to prepare (A) polyimide precursors, for example, 2-hydroxyethyl methacrylate (HEMA ), 2-propenyl oxyethanol, 1-propenyl oxy-3-propanol, 2-propenyl amine ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, acrylic 2-hydroxy- 3-methoxypropyl ester, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate Hydroxy-3-tert-butoxypropyl, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethanol, 1-methacryloxy-3-propanol, 2-Methacrylamide ethanol, hydroxymethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, methacrylic acid 2 -Hydroxy-3-phenoxypropyl ester, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy methacrylate- 3-cyclohexyloxy propyl ester and the like.

It can also be used by mixing a part of alcohols without unsaturated double bonds with the above-mentioned alcohols with photopolymerizable unsaturated double bonds. Examples of alcohols without unsaturated double bonds include methanol, ethanol, and n-propanol. , Isopropanol, n-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentanol, 1-heptanol, 2-heptanol, 3-heptanol, 1- Octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol Wait.

In addition, as a polyimide precursor, a non-photosensitive polyimide precursor prepared only with the above-mentioned alcohols having no unsaturated double bond and a photosensitive polyimide precursor may be mixed and used. From the viewpoint of resolution, it is preferable that the non-photosensitive polyimide precursor is 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

In the preparation of the polyimide precursor, the content of the organic group represented by the general formula (2) in the polyimide precursor relative to the total content of _{R 1} , R ₂ , and R _{6 is preferably 50} More than mol%. If the content of the organic group of the general formula (2) exceeds 50 mol%, the desired photosensitive characteristics can be obtained, which is preferable. In the preparation of the photosensitive resin composition, the content of the organic group of the general formula (2) in the photosensitive resin composition relative to _{the total content of R 1} , R ₂ and R ₆ is preferably 75 mol% or more.

The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol are dissolved and mixed in the presence of a basic catalyst such as pyridine and in the following reaction solvent or solvent at a temperature of 20-50℃ for 4-10 hours. By this, the esterification reaction of the acid anhydride proceeds, and the desired acid/ester body can be obtained.

As the above-mentioned reaction solvent, it is preferably one that dissolves the acid/ester body and the polyimide precursor that is the polyimide precursor of the acid/ester body and diamines. The reaction solvent includes, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfene, tetramethylurea, γ-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, methyl acetate, acetic acid Ethyl, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methylene chloride, 1,2-dichloroethane, 1,4-dichlorobutane , Chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. These can be used alone or in combination of two or more as needed.

(Preparation of Polyimide Precursor) Under ice-bath cooling, the above acid/ester body (typically a reaction solvent or a solution in a solvent) is added and mixed with a suitable dehydrating condensing agent, such as dicyclohexylcarbodiamide Imine, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N After the acid/ester body is made into a polyacid anhydride by'-dibutyl diamide carbonate etc., the _{diamines containing the divalent organic group Y 1} which are suitable for use in this embodiment are added dropwise. In addition It is formed by dissolving or dispersing in a solvent and undergoing condensation polymerization of amide to obtain the target polyimide precursor. As the dehydration condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di -1,2,3-benzotriazole, N,N'-dibutylimid carbonate, etc. As an alternative, for the above-mentioned acid/ester, the acid part is chlorinated with sulfite chloride, etc., and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the target polyimide precursor. .

_{The diamines containing the divalent organic group Y 1} suitable for use in this embodiment are represented by diamines having the structure represented by the above-mentioned general formula (21), for example: p-phenylenediamine, m-phenylene Diamine, 4,4-diaminodiphenyl ether (DADPE) (4,4'-oxydiphenylamine (ODA)), 3,4'-diaminodiphenyl ether, 3,3'-diamino Diphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4' -Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl, 3,4' -Diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-di Aminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4- Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4 -Aminophenoxy) phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, 4,4-bis(4-aminophenoxy)biphenyl, 4,4 -Bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl))benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2- Bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl))hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-tolidine , 9,9-bis(4-aminophenyl) sulfide, and a part of the hydrogen atoms on the benzene ring thereof are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., For example, 3,3'-dimethyl-4,4'-diamino biphenyl, 2,2'-dimethyl-4,4'-diamino biphenyl (2,2'-dimethyl biphenyl) Benzene-4,4'-diamine (m-TB)), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4 '-Diaminodiphenylmethane, 3,3'-Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-Diamino-2,2'-bis(trifluoromethyl)-biphenyl, and mixtures thereof, etc.

In order to improve the adhesion between the photosensitive resin layer formed on the substrate by coating the photosensitive resin composition on the substrate and various substrates, it can also be used when preparing (A, A1) polyimide precursors. Diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, etc. Copolymerization.

After the amine polycondensation reaction is completed, if necessary, the water absorption by-product of the dehydration condensing agent coexisting in the reaction liquid is filtered and separated, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is poured into the reaction liquid or the resulting polymerization In the composition of the polymer, the polymer composition is analyzed, and the operations of re-dissolution and re-precipitation are repeated to purify the polymer and vacuum-dried to isolate the target polyimide precursor. In order to improve the degree of purification, the polymer solution can also be passed through a column filled with anion and/or cation exchange resin swelled with a suitable organic solvent to remove ionic impurities.

When using gel permeation chromatography to measure the weight average molecular weight in terms of polystyrene, the molecular weight of the (A, A1) polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, More preferably, it is 18,000-40,000. When the weight average molecular weight is above 8,000, the mechanical properties are good. When the weight average molecular weight is below 150,000, the dispersibility in the developer is good, and the resolution of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight is calculated from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to choose from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

(B) Compounds with urethane bond or urea bond (B) The compound having a urethane bond or a urea bond includes at least one selected from the group consisting of a urethane bond and a urea bond in the molecular structure. In one embodiment, by containing the (B) compound, it is possible to improve the adhesion with the molding resin and/or the in-plane uniformity when it is formed in a multilayer form. However, this effect is manifested by using the (D) solvent together with the urethane/urea compound.

(B) The compound should just have a urethane bond and/or a urea bond in a molecular structure. Among them, from the viewpoint of suppression of pores on the Cu surface or chemical resistance, the (B) compound preferably has a urea bond. In addition, the compound having a urea bond may be the (K) urea compound described below.

{式中，R₇ 及R₈ 分別獨立地為可包含雜原子之碳數1～20之1價有機基，並且R₉ 及R₁₀ 分別獨立為氫原子、或可包含雜原子之碳數1～20之1價有機基} [化31]

{式中，R₁₁ 及R₁₂ 分別獨立地為可包含雜原子之碳數1～20之1價有機基，並且R₁₃ 為可包含雜原子之碳數1～20之2價有機基}Among the compounds having a urea bond, the compound represented by the following general formula (3) or (4) is more preferable from the viewpoint of developability. [化30]

{In the formula, R ₇ and R ₈ are each independently a monovalent organic group with 1 to 20 carbon atoms that may contain a hetero atom, and R ₉ and R ₁₀ are each independently a hydrogen atom or a carbon number that may contain a hetero atom 1 ~20 monovalent organic groups} [化31]

{In the formula, R ₁₁ and R ₁₂ are each independently a monovalent organic group with _{1 to 20 carbons that may contain a heteroatom, and R 13} is a divalent organic group with 1 to 20 carbons that may contain a heteroatom}

Examples of the hetero atom in this embodiment include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. In the formula (3), R ₇ and R _{8 may} each independently be a monovalent organic group having 1 to 20 carbon atoms that may include a hetero atom, and from the viewpoint of developability, it is more preferable to include an oxygen atom. The carbon number of R ₇ and R ₈ may be 1-20, and from the viewpoint of heat resistance, the carbon number is preferably 1-10, more preferably 3-10.

In formula (3), R ₉ and R ₁₀ are each independently a hydrogen atom, or a monovalent organic group with 1 to 20 carbon atoms that may contain a hetero atom, and from the viewpoint of developability, a hydrogen atom is more preferable Or contain oxygen atoms. The carbon number of R ₉ and R ₁₀ only needs to be 1-20, and from the viewpoint of heat resistance, the carbon number is preferably 1-10, and more preferably 3-10.

Moreover, in formula (4), R ₁₁ and R _{12 may} each independently be a monovalent organic group having 1 to 20 carbon atoms that may include a hetero atom, and from the viewpoint of developability, it is more preferable to include an oxygen atom. The carbon number of R ₁₁ and R ₁₂ may be 1-20, and from the viewpoint of heat resistance, the carbon number is preferably 1-10, more preferably 3-10. In the formula (4), R ₁₃ may be a divalent organic group with 1 to 20 carbon atoms that may contain a hetero atom. From the viewpoint of suppressing the generation of cracks or elongation in a reliability test, it is more preferable to contain At least 1 oxygen atom. The carbon number of R ₁₃ may be from 1 to 20, and from the viewpoint of containing a heteroatom, it is preferably 2 or more, and from the viewpoint of heat resistance, it is preferably from 1 to 18.

In this embodiment, the (B) compound preferably further has at least one functional group selected from the group consisting of (meth)acrylic group, hydroxyl group, and amino group, and more preferably has (methyl) Acrylic acid base.

The reason why the adhesion to the molding resin or the in-plane uniformity when formed into multiple layers is good due to the inclusion of the (B) compound and (D) solvent of the present embodiment is not clear, but the present inventors believe that As follows. That is, normally, the negative photosensitive resin composition is heated and cured at a relatively low temperature of 180°C or less, and therefore there is a tendency that the conversion of the polyimide precursor to the polyimide is insufficient. In particular, if (G) a polymerizable unsaturated monomer having 3 or more polymerizable functional groups is included, the above tendency becomes more pronounced. On the other hand, since the negative photosensitive resin composition of this embodiment contains the urethane/urea compound (B), a part of the compound (B) is thermally decomposed to generate amines, etc. Promote the conversion of polyimide precursors to polyimide. Furthermore, in a preferred embodiment, the compound (B) further has a (meth)acrylic acid group. Therefore, especially in the case of a negative photosensitive resin composition, the compound (B) is irradiated with light The side chain part of the imine precursor reacts and cross-links, so it is more likely to exist in the vicinity of the polyimine precursor, and the conversion efficiency can be dramatically improved. Therefore, in the production of polyimide or hardened embossed pattern of this embodiment, although the heat hardening is performed at a low temperature, the conversion to polyimide is almost completed, so the cyclization reaction will not continue. , No shrinkage stress is generated, so that the state of high adhesion can be maintained. In addition, since the conversion to polyimide is almost complete, when the photosensitive resin composition is applied and pre-baked in order to form the second polyimide film on the first polyimide film, The first layer of polyimide film has sufficient solvent resistance, so it fully exhibits in-plane uniformity.

In this embodiment, when the (B) compound further has a (meth)acryloyl group, the (meth)acryloyl group equivalent of the (B) compound is preferably 150 to 400 g/mol. By making the (meth)acrylic acid equivalent of the (B) compound 150 g/mol or more, there is a tendency that the chemical resistance of the negative photosensitive resin composition becomes better, and by making the (B) compound The (meth)acrylic acid group equivalent is 400 g/mol or less, and the developability tends to become better. (B) The lower limit of the (meth)acrylic acid equivalent of the compound is more preferably 200 g/mol or more, 210 g/mol or more, 220 g/mol or more, or 230 g/mol or more, and more preferably 240 g/mol or more, or 250 g/mol or more, the lower limit is more preferably 350 g/mol or less, or 330 g/mol or less, and still more preferably 300 g/mol or less. (B) The (meth)acrylic acid equivalent of the compound is more preferably 210 to 400 g/mol, and particularly preferably 220 to 400 g/mol.

{式中，R₃ 為氫原子或甲基，A為選自由-O-、-NH-、及-NL₄ -所組成之群中之一個基，L₄ 為碳數1～12之1價有機基，Z₁ 為碳數2～24之m₂ 價有機基，Z₂ 為碳數2～8之2價有機基，並且m₂ 為1～3之整數}The urethane/urea compound (B) used in this embodiment is preferably a (meth)acrylic acid group-containing urethane/urea having a structure represented by the following general formula (b3) Compound. [化32]

{In the formula, R ₃ is a hydrogen atom or a methyl group, A is a group selected from the group consisting of _{-O-, -NH-, and -NL 4 -, and L 4} is monovalent with 1 to 12 carbon atoms Organic group, Z _{1 is an m 2} valent organic group with 2 to 24 carbons _{, Z 2} is a divalent organic group with 2 to 8 carbons, and m ₂ is an integer of 1 to 3}

In the formula (b3), R _{3 may} be a hydrogen atom or a methyl group, and from the viewpoint of developability, a methyl group is preferable. Z ₁ only needs to be an m ₂ valent organic group having 2-24 carbon atoms, and the carbon number is preferably 2-20. Here, Z ₁ may include heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. If _{the carbon number of Z 1} is 2 or more, the chemical resistance of the negative photosensitive resin composition tends to be good, and if the carbon number is 20 or less, the developability tends to be good. The carbon number of Z ₁ is more preferably 3 or more, still more preferably 4 or more, more preferably 18 or less, and still more preferably 16 or less. Z ₂ may be a divalent organic group having 2 to 8 carbon atoms. Here, Z ₂ may include heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. If _{the carbon number of Z 2} is 2 or more, the chemical resistance of the negative photosensitive resin composition tends to be good, and if the carbon number is 8 or less, the heat resistance tends to be good. The carbon number of Z ₂ is preferably 6 or less, more preferably 4 or less. A is a group selected from the group consisting of -O-, -NH-, and -NL ₄ -{where L ₄ is a monovalent organic group having 1 to 12 carbons}. From the viewpoint of chemical resistance, A is preferably -NH- or NL ₄ -.

The method for producing the (meth)acrylic acid group-containing urea/urethane compound of the above-mentioned general formula (b3) can be, for example, by combining an isocyanate compound represented by the following general formula, an amine and/or a hydroxyl group-containing The compound is obtained by reaction. [化33]

[化35]

[化36]

[化37]

[化38]

[化39]

[化40]

[化41]

[化42]

[化43]

Among the (B) compounds described above, from the viewpoints of chemical resistance, void suppression, and developability, they are particularly preferably selected from the following formulas (b4) to (b7), and (b11) to (b16) At least one compound in the group consisting of. Furthermore, the compounds represented by the following formulas (b4) to (b7) and (b11) to (b16) are also an embodiment of the present invention. [化34]

[化35]

[化36]

[化37]

[化38]

[化39]

[化40]

[化41]

[化42]

[化43]

In another embodiment, tetramethylurea can be used as (B) a compound having a urea bond or (K) a urea compound.

The (B) compound in this embodiment may be used individually by 1 type, or may mix and use 2 or more types. The compounding amount of the (B) compound is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less relative to 100 parts by mass of the polyimide precursor (A, A1). From the viewpoint of photosensitivity and pattern properties, the blending amount of the above (B) is 0.1 parts by mass or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition, it is 30 parts by mass The following.

(C1) Sensitizer The photosensitive resin composition of this embodiment contains (C1) a photosensitive agent. In one embodiment, in order to promote the hardening of the relief pattern by light irradiation, the photosensitizer may be a photopolymerization initiator, for example, the (C) photopolymerization initiator of the first to third aspects.

(C1) The compounding amount of the photosensitizer is preferably 0.1 parts by mass or more and 20 parts by mass, more preferably 1 part by mass or more and 8 parts by mass or less relative to 100 parts by mass of the polyimide precursor (A, A1). From the viewpoint of photosensitivity or pattern properties, the compounding amount of the above-mentioned (C1) photosensitive agent is preferably 0.1 parts by mass or more. From the viewpoint of the physical properties of the photosensitive resin layer after the photosensitive resin composition is cured, the above-mentioned (C1) The compounding amount of the photosensitizer is preferably 20 parts by mass or less.

、2-甲基-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

、二乙基-9-氧硫𠮿

等9-氧硫𠮿

衍生物；苯偶醯、苯偶醯二甲基縮酮、及苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物；安息香、及安息香甲醚等安息香衍生物；1-苯基-1,2-丁二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰苯甲醯基)肟、1,3-二苯基丙三酮-2-(鄰乙氧基羰基)肟、及1-苯基-3-乙氧基丙三酮-2-(鄰苯甲醯基)肟等肟類；N-苯基甘胺酸等N-芳基甘胺酸類；全氯苯甲醯等過氧化物類；芳香族聯咪唑類類；二茂鈦類；以及α-(正辛烷磺醯氧基亞胺基)-4-甲氧基苄基氰化物等光酸產生劑類等。於上述光聚合起始劑之中，尤其是就光感度之觀點而言，更佳為肟類。(C) Photopolymerization initiator The photopolymerization initiator is preferably a photoradical polymerization initiator. As a photo-radical polymerization initiator, benzophenone, methyl phthalate, 4-benzyl-4'-methyl diphenyl ketone, dibenzyl ketone, quinone, etc. Benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives; 9-oxygen Sulfur

, 2-Methyl-9-oxysulfur 𠮿

, 2-isopropyl-9-oxysulfur 𠮿

, Diethyl-9-oxysulfur 𠮿

Wait 9-oxysulfur 𠮿

Derivatives; benzil derivatives such as benzil, benzil dimethyl ketal, and benzil-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1- Phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl -1,2-Propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzyl)oxime, 1,3-diphenyl Oxyglycerol-2-(o-ethoxycarbonyl)oxime and 1-phenyl-3-ethoxyglycerol-2-(o-benzyl)oxime; N-phenylglycerol N-arylglycines such as amino acids; peroxides such as perchlorobenzoyl; aromatic biimidazoles; titanocene; and α-(n-octanesulfonyloxyimino)- Photo acid generators such as 4-methoxybenzyl cyanide, etc. Among the above-mentioned photopolymerization initiators, oximes are more preferable from the viewpoint of photosensitivity.

With respect to 100 parts by mass of (A, A1) polyimide precursor, the compounding amount of (C) photopolymerization initiator is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass the following. Regarding the above-mentioned compounding amount, it is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or pattern properties, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition, it is preferably 20 parts by mass or less.

(D) At least one solvent selected from the group consisting of 3-methoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide The (D) solvent of this embodiment is at least one of 3-methoxy-N,N-dimethylpropanamide or 3-butoxy-N,N-dimethylpropanamide. By using the above-mentioned solvent, the effect of the above-mentioned (B) urea/urethane compound is exhibited. The reason for this is not clear, but it is presumed that (B) the urea/urethane compound is thermally decomposed to promote the conversion to polyimide as described above. On the other hand, it is believed that (B) urea/urethane compound has a high cohesive force. Therefore, if the solvent volatilizes during thermal hardening, agglomeration will occur and the decomposition will be difficult. In this case, if the specific 3-form is used The (D) solvent of oxy-N,N-dimethylpropanamide or 3-butoxy-N,N-dimethylpropanamide, then the interaction between urea/urethane compound and solvent The effect is large, so condensation is difficult to occur, and the conversion of polyimide is easy to proceed, so the adhesion is improved. In addition, since the aggregation of the compound (B) is suppressed, the elongation after the reliability test tends to increase. This effect is in the case of using 3-methoxy-N,N-dimethylpropanamide as the solvent (D) in the following examples, and the use of 3-butoxy-N,N-di When methyl propionamide is used as the solvent (D), it is obtained separately. Then, based on the mechanism estimated as described above, it is understood that this effect can also be obtained when the two are used in combination as the (D) solvent.

As the (D) solvent of this embodiment, the following solvents (hereinafter also referred to as "other solvents") may be included within a range that does not adversely affect performance. In the second aspect, other solvents can be (A, A1) polyimide precursors, (B) compounds having urethane bonds or urea bonds, (C) photopolymerization initiators (G) A solvent in which the polymerizable unsaturated monomer having 3 or more polymerizable functional groups uniformly dissolves or suspends.

As other solvents, for example, amines, sulfites, ureas (except for the compound containing a urea bond in the above (B) or the following (K) urea compound), ketones, esters, and lactones Classes, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, etc. More specifically, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformaldehyde can be used. Amide, dimethyl sulfide, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, lactic acid Ethyl ester, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, tetrahydrofuran methanol, ethylene glycol dimethyl ether, diethyl Glycol dimethyl ether, tetrahydrofuran, quinoline, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane , Benzene, toluene, xylene, mesitylene, etc. On the other hand, relative to 100 parts by mass of the polyimide precursor (A, A1), the content of other solvents is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. In addition, the content of other solvents is preferably less than the content of (D) solvent.

In the negative photosensitive resin composition of the present embodiment, the amount of (D) solvent used is preferably 10 to 1000 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1), and more preferably 100 to 700 parts by mass, more preferably in the range of 125 to 500 parts by mass. When 3-methoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide are used in combination, the total usage amount is preferably in the above-mentioned range.

(D1) Solvent The (D1) solvent of the third aspect can uniformly suspend or dissolve (A, A1) polyimide precursor, (B) urethane/urea compound, and (C) photopolymerization initiator.

(D1) Solvents include: amines, sulfites, ureas (except for the compound containing the urea bond in (B) above), ketones, esters, lactones, ethers, halogenated hydrocarbons Types, hydrocarbons, and alcohols, etc. More specifically, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3- Butoxy-N,N-dimethylpropanamide, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone , Methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylglycol, tetrahydrofuran methanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 𠰌line, dichloromethane, 1 , 2-Dichloroethane, 1,4-Dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. (D1) A solvent can be used individually by 1 type, or in combination of 2 or more types.

In the negative photosensitive resin composition of the present embodiment, the total usage amount of all solvent components including (D) solvent, other solvents, and (D1) solvents described above is relative to (A, A1) polyamide 100 parts by mass of the imine precursor is preferably in the range of 10 to 1000 parts by mass, more preferably 100 to 700 parts by mass, and still more preferably 125 to 500 parts by mass.

(D2) Solvent The photosensitive resin composition of this embodiment may contain (D2) a solvent. (D2) Solvents include amines, sulfites, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, and the like. As the (D2) solvent, it is preferable to use a polar organic solvent in terms of the solubility of the (A, A1) polyimide precursor.

As the (D2) solvent, specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N- Dimethyl acetamide, dimethyl sulfide, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate Ester, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, tetrahydrofuran methanol, ethylene glycol dimethyl ether, Tetrahydrofuran, dichloromethane, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, dichloromethane Toluene, mesitylene, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-ring Hexyl-2-pyrrolidone, 2-octanone, etc., can be used alone or in combination of two or more kinds. Among them, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesion to the substrate, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and tetramethylurea are preferred. , Butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenylglycol, and tetrahydrofuran methanol.

Among such (D2) solvents, those that completely dissolve the resulting polymer are particularly preferred. Examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N- Dimethylformamide, dimethyl sulfide, tetramethylurea (wherein, when used as the above (B) component or the following (K) component, it is excluded from the (D2) component), γ -Butyrolactone and so on. The solvent may be one type, or two or more types of solvents may be mixed and used.

(D2) The solvent can be used within the following range depending on the required coating film thickness and viscosity of the photosensitive resin composition, ie, 30 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1) -1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass, more preferably 100 parts by mass to 860 parts by mass, still more preferably 120-700 parts by mass, particularly preferably 125-500 parts by mass.

From the viewpoint of improving the storage stability of the photosensitive resin composition, the solvent (D2) containing alcohols is preferred. Suitable alcohols are typically alcohols with alcoholic hydroxyl groups in the molecule and no olefinic double bonds. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, Alkyl alcohols such as isobutanol and tertiary butanol; lactate esters such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol- Propylene glycol monoalkyl ethers such as 1-(n-propyl) ether and propylene glycol-2-(n-propyl) ether; mono-alcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol-n-propyl ether; 2-hydroxyisobutyrates; glycols such as ethylene glycol and propylene glycol. Among them, preferred are lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethanol, especially ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, And propylene glycol-1-(n-propyl) ether is more preferable.

When (D2) the solvent contains alcohols without olefinic double bonds, the content of alcohols without olefinic double bonds in all solvents is based on the mass of the total solvent, and is preferably 5% by mass to 50% by mass , More preferably 10% by mass to 30% by mass. When the above-mentioned content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition becomes good. On the other hand, when it is 50% by mass or less, (A , A1) The solubility of the polyimide precursor becomes better, so it is better.

(E) Rust inhibitor The negative photosensitive resin composition of this embodiment may further contain (E) a rust inhibitor. As the rust inhibitor, any rust inhibitor may be used as long as it can prevent rust from a metal, and a nitrogen-containing heterocyclic compound may be mentioned. Examples of nitrogen-containing heterocyclic compounds include azole compounds, purines, or purine derivatives, and the like.

Examples of azole compounds include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-benzene -1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5 -Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5- Diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl)-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl 5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tertiary pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'- Hydroxy-5'-third octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzene O-triazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole , 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole, etc.

As the azole compound, particularly preferred examples include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Moreover, these azole compounds may be used individually by 1 type, and may mix and use 2 or more types.

(E) The rust inhibitor may include purine, or a derivative thereof. Moreover, as purine derivatives contained in (E) rust inhibitor, for example, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-di Aminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2- Fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H -Purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyl adenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chloro Phenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-aza Heteropurine, 8-azaxanthine, 8-azahypoxanthine, etc., and their derivatives.

When the negative photosensitive resin composition contains an azole compound, or a purine or a purine derivative, the blending amount is preferably 0.05-5 mass parts with respect to 100 parts by mass of the polyimide precursor (A, A1) Parts, or 0.05-20 parts by mass, more preferably 0.1-5 parts by mass, or 0.1-20 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the polyimide precursor (A, A1) is 0.05 parts by mass or more, the negative photosensitive resin composition of this embodiment is formed on copper or In the case of the copper alloy, the discoloration of the copper or copper alloy surface is suppressed. On the other hand, when the azole compound is 5 parts by mass or less or 20 parts by mass or less, the light sensitivity is excellent.

When the negative photosensitive resin composition of the present embodiment contains (E) a rust inhibitor, the formation of voids in the Cu layer is particularly suppressed. The reason for the effect is not clear, but it is believed that the reason is that the rust inhibitor present on the Cu surface and the (meth)acrylic acid group contained in the preferred embodiment of the urethane/urea compound , Hydroxyl, alkoxy, or amine groups interact to form a dense layer near the Cu interface.

(F) Silane coupling agent The negative photosensitive resin composition of this embodiment may further contain (F) a silane coupling agent. As the silane coupling agent, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-glycidoxysilane can be mentioned. Propylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxy Propyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropyl silane, diethoxy-3-glycidoxypropylmethyl silane, N-(3-diethoxymethyl Silyl propyl) succinimide, N-[3-(triethoxysilyl) propyl] phthalic acid, benzophenone-3,3'-bis(N- [3-Triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide) -2,5-Dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3 -Ureayl propyl triethoxy silane, and 3-(trialkoxy silyl) propyl succinic anhydride and other silane coupling agents.

As the silane coupling agent, more specifically, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace S810), 3 -Mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, Azmax Co., Ltd.) Manufactured by Co., Ltd.: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethyl methyldimethoxysilane (manufactured by Azmax Co., Ltd.: product (Name SIM6473.0), 3-mercaptopropyl diethoxy methoxy silane, 3-mercaptopropyl ethoxy dimethoxy silane, 3-mercaptopropyl tripropoxy silane, 3-mercaptopropyl Diethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane , 2-Mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane Silane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, etc.

In addition, as a silane coupling agent, more specifically, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: product Name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl) ) Urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxy) Silylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3- Methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N- (3-Tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N -(3-Dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl) Urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (Manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyl trimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyl trimethoxysilane (Azmax Co., Ltd. Company manufacture: trade name SLA0599.1) aminophenyl trimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), etc.

Moreover, as a silane coupling agent, more specifically, 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxysilyl) Ethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)- Tertiary butyl carbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropyl Oxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, tetra-tertiary butoxysilane, tetra(methoxyethoxysilane), tetra(methoxy-n-propoxy) Silane), tetra(ethoxyethoxysilane), tetra(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, Bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethyl) Oxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di- Tributoxydiethoxysilane, di-isobutoxyaluminumoxytriethoxysilane, phenylsilantriol, methylphenylsilanediol, ethylphenylsilanediol, n-propyl Phenyl phenyl silane diol, isopropyl phenyl silane diol, n-butyl diphenyl silane diol, isobutyl phenyl silane diol, tertiary butyl phenyl silane diol, diphenyl silane two Alcohol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, Isopropyl methyl phenyl silanol, n-butyl methyl phenyl silanol, isobutyl methyl phenyl silanol, tertiary butyl methyl phenyl silanol, ethyl n-propyl phenyl silanol, ethyl isopropyl Phenyl silanol, n-butyl ethyl phenyl silanol, isobutyl ethyl phenyl silanol, tertiary butyl ethyl phenyl silanol, methyl diphenyl silanol, ethyl diphenyl silanol Alcohol, n-propyl diphenyl silanol, isopropyl diphenyl silanol, n-butyl diphenyl silanol, isobutyl diphenyl silanol, tertiary butyl diphenyl silanol, and three Phenyl silanol and so on. The silane coupling agents listed above may be used alone or in combination of plural kinds.

Among the above-mentioned silane coupling agents, from the standpoint of storage stability, phenyl silane triol, trimethoxyphenyl silane, trimethoxy (p-tolyl) silane, diphenyl silane diol, and dimethyl siloxane are preferred. Oxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent having a structure represented by the following formula. [化44]

As the compounding amount when the silane coupling agent is used, it is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1). When the negative photosensitive resin composition of the present embodiment contains the (F) silane coupling agent, the formation of voids in the Cu layer is particularly suppressed. The reason for the effect is not clear, but it is believed that the reason is: the (meth)acrylic acid contained in the preferred embodiment of the silane coupling agent and the urethane/urea compound that are concentrated on the Cu surface Groups, hydroxyl groups, alkoxy groups, or amine groups interact to form a dense layer near the Cu interface.

(G) Polymerizable unsaturated monomers with more than 3 polymerizable functional groups In one embodiment, the photosensitive resin composition contains a polymerizable unsaturated monomer having 3 or more polymerizable functional groups in the molecular structure as the (G) component. The photosensitive resin composition can improve storage stability and chemical resistance by containing (G) a polymerizable unsaturated monomer.

In this specification, the "polymerizable functional group" refers to a functional group that can be bonded to other functional groups. The 3 or more polymerizable functional groups in the (G) polymerizable unsaturated monomer are preferably at least one functional group selected from the group consisting of (meth)acrylic groups, hydroxyl groups, and amino groups. Thereby, the effect of the present invention can be easily obtained.

Furthermore, in one embodiment, from the viewpoint of developability, the polymerizable functional group is preferably a (meth)acryloyl group.

As such (G) polymerizable unsaturated monomers, for example, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate (Base) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate, etc.

Furthermore, in the (G) polymerizable unsaturated monomer, one of the 3 or more polymerizable functional groups may be a (meth)acrylic acid group, or two of the (meth)acrylic acid groups may be used. Three or more (meth)acrylic groups may be used, and when four or more polymerizable functional groups are included, all of the four polymerizable functional groups may be (meth)acrylic groups. When three or more polymerizable functional groups include a plurality of (meth)acrylic groups, the plurality of (meth)acrylic groups may be the same or different from each other.

(G) The functional group equivalent (g/mol) of the polymerizable unsaturated monomer having 3 or more polymerizable functional groups in this embodiment is preferably 50-300. In addition, when the (G) polymerizable unsaturated monomer contains a (meth)acryloyl group, the (meth)acryloyl group equivalent is preferably 50-300, more preferably 70-250. Thereby, it is easier to obtain the effect of the present invention. Furthermore, the functional group equivalent (g/mol) in this embodiment is a value obtained by dividing the molecular weight by the number of functional groups.

The (G) polymerizable unsaturated monomer used in this embodiment may be one type or two or more types.

(G) The compounding amount of the polymerizable unsaturated monomer having 3 or more polymerizable functional groups is preferably 1 part by mass or more and 50 parts by mass relative to 100 parts by mass of the (A, A1) polyimide precursor Parts or less, more preferably 3 parts by mass or more and 45 parts by mass or less. From the viewpoint of polymerizability, the above-mentioned compounding amount is more preferably 5 parts by mass or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition, it is more preferably 40 parts by mass the following.

(H) Other ingredients The negative photosensitive resin composition of the present embodiment may further contain components other than the above-mentioned (A) to (G) components. Examples of components other than the (A) to (G) components include: (A, A1) resin components other than polyimide precursors; epoxy resins; adhesive additives; thermal alkali generators, hindered phenol compounds, Organic titanium compounds, sensitizers, photopolymerizable unsaturated monomers, thermal polymerization inhibitors, etc.

From the viewpoint of obtaining a cured film with a high degree of crosslinking, the photosensitive resin composition may further contain an epoxy resin. The amount of the epoxy resin is preferably 0.01-25 parts by mass, more preferably 0.1-15 parts by mass, and still more preferably 0.1-10 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1). When using the (I) compound derived from an epoxy resin, the epoxy resin of a raw material may be included in the photosensitive resin composition, and it is easier to adjust the amount of the epoxy resin to the above-mentioned range.

In one embodiment, the photosensitive resin composition may further contain (A, A1) resin components other than the polyimide precursor. As the resin component that can be contained in the photosensitive resin composition, for example, polyimide, polyazole, polyazole precursor, phenol resin, polyamide, epoxy resin, silicone resin, acrylic Resin etc. The blending amount of these resin components is preferably in the range of 0.01 parts by mass to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1).

When (A, A1) polyimide precursors and polyazole precursors are used to prepare a positive photosensitive resin composition, as a positive photosensitive material, a compound having a quinonediazide group, such as Compounds with 1,2-benzoquinonediazide structure or 1,2-diazide naphthoquinone structure, etc.

Thermal alkali generator The photosensitive resin composition of this embodiment may contain an alkali generator. The alkali generator refers to a compound that generates alkali by heating. By containing the thermal base generator, the imidization of the photosensitive resin composition can be further promoted.

The type of the thermal base generator is not specifically defined, and examples include amine compounds protected with a tertiary butoxycarbonyl group, or the thermal base generator disclosed in International Publication No. 2017/038598. However, it is not limited to them, and other well-known thermal alkali generators can also be used.

Examples of the amine compound protected by the tertiary butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4- Amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino -2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino- 1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl Base] benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidol, 2-pyrrolidine methanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4 -(3-Hydroxyphenyl)piperidine, 4-piperidine methanol, 3-piperidine methanol, 2-piperidine methanol, 4-piperidine ethanol, 2-piperidine ethanol, 2-(4-piperidinyl) -2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethyl) Amine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5, diethylene glycol bis(3-aminopropyl ) Ether, 1,11-diamino-3,6,9-trioxaundecane, or amino acid and its derivatives whose amine group is protected by tertiary butoxycarbonyl, but not limited Yu Qi and so on.

The blending amount of the thermal alkali generator is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyimide precursor (A, A1). Regarding the above-mentioned compounding amount, from the viewpoint of the effect of accelerating the imidization, it is preferably 0.1 parts by mass or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition, it is preferably 20 Parts by mass or less.

Hindered phenol compounds In order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of hindered phenol compounds include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, and octadecyl-3-(3 ,5-Di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4, 4'-Methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'- Butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyl -Phenylpropanamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6 -Tertiary butyl phenol), pentaerythritol group-tetra[3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate], tris-(3,5-di-tertiary butyl) 4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) Benzene etc.

In addition, as hindered phenol compounds, for example, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris-2 ,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tertiarybutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3, 5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-secondbutyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy -2,6-Dimethylbenzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-triethyl) Methyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5 -Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-Tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H ,5H)-Triketone, 1,3,5-tris(4-tertiarybutyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triketone -2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)- 1,3,5-tris-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tertiarybutyl-6-ethyl-3-hydroxy- 2,5-Dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tertiary butyl) -5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione , 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H ,5H)-triketone, and 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2 ,4,6-(1H,3H,5H)-triketone and so on. Among the hindered phenol compounds listed above, 1,3,5-tris(4-tertiarybutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5- Three 𠯤-2,4,6-(1H,3H,5H)-triketone etc.

The compounding amount of the hindered phenol compound is preferably 0.1-20 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1), and more preferably 0.5-10 parts by mass from the viewpoint of photosensitivity characteristics. When the compounding amount of the hindered phenol compound relative to 100 parts by mass of the polyimide precursor (A, A1) is 0.1 parts by mass or more, for example, the photosensitive resin composition of the present embodiment is formed on copper or copper alloy In the case of objects, discoloration and corrosion of copper or copper alloys are prevented. On the other hand, when it is 20 parts by mass or less, the light sensitivity is excellent.

Organic Titanium Compound The negative photosensitive resin composition of this embodiment may contain an organic titanium compound. By including the organic titanium compound, even when it is cured at a low temperature of about 250° C., a photosensitive resin layer with excellent chemical resistance can be formed.

As an organotitanium compound that can be used, an organic chemical substance is bound to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are listed in I) to VII) below:

I) Titanium chelate compound: Among them, in order to obtain the storage stability and good pattern of the negative photosensitive resin composition, it is more preferably a titanium chelate compound having two or more alkoxy groups. Specific examples are: bis(triethanolamine)titanium diisopropoxide, bis(2,4-glutaric acid)di(n-butanol)titanium, bis(2,4-glutaric acid)titanium diisopropoxide, double (Tetramethylpimelic acid) titanium diisopropoxide, bis(ethylacetate) titanium diisopropoxide, and the like.

II) Titanium tetraalkoxide compound: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium tetramethoxypropoxide, titanium tetramethylphenolate, tetra(n-nonyl alcohol) titanium, tetra(n-propanol) titanium, tetrastearyl titanium, tetrakis[bis{2,2-(allyloxymethyl基)Butanol}]Titanium and so on.

III) Titanocene compounds: for example (pentamethylcyclopentadienyl)titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) ) Titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.

IV) Monoalkoxy titanium compounds: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylbenzene sulfonic acid) titanium isopropoxide, and the like.

V) Titanium oxide compound: for example, titanyl bis(glutarate), titanyl bis(tetramethylpimelate), titanyl phthalocyanine, and the like.

VI) Titanium tetraacetylpyruvate compound: for example, titanium tetraacetylpyruvate.

VII) Titanate coupling agent: for example, isopropyl tris(dodecylbenzenesulfonyl) titanate and the like.

Among them, from the viewpoint of exerting better chemical resistance, the organic titanium compound is preferably selected from the group consisting of I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound. At least one compound in the group. Particularly preferred are bis(ethylacetate) titanium diisopropoxide, tetra(n-butoxide)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-di Fluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

When the organotitanium compound is blended, the blending amount is preferably 0.05-10 parts by mass, more preferably 0.1-2 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1). When the compounding amount of the organotitanium compound is 0.05 parts by mass or more, it exhibits good heat resistance and chemical resistance. On the other hand, when it is 10 parts by mass or less, the storage stability is excellent.

Sensitizer In order to improve the photosensitivity, the negative photosensitive resin composition of this embodiment may optionally contain a sensitizer. As the sensitizer, for example, Michelone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylamino)benzylidene )Cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methyl Cyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylindene Ketone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenyl)-benzothiazole, 2-(p-dimethylaminophenyl vinylidene) Benzothiazole, 2-(p-dimethylaminophenyl vinylidene)isonaphththiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4 '-Diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin , 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylamine Coumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-Phenylethanolamine, 4-Phenylbenzophenone, Isoamyl Dimethylaminobenzoate, Isoamyl Diethylaminobenzoate, 2-Mercaptobenzimidazole, 1-Phenyl- 5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylamino styryl) benzo azole, 2-(p-dimethylamino styryl) benzothiazole, and 2 -(P-dimethylamino styryl) naphtho(1,2-d)thiazole, 2-(p-dimethylamino styryl) styrene, etc. These etc. may be used individually by 1 type, or may be used in combination of a plurality of types, for example, combining 2 to 5 types.

When the photosensitive resin composition contains a sensitizer, the compounding amount is preferably 0.1-25 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1).

Photopolymerizable unsaturated monomer In order to improve the resolution of the relief pattern, the negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond (photopolymerizable unsaturated monomer). When the following (I) component is used, the (I) component excludes the photopolymerizable unsaturated monomer. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferred, and examples thereof include diethylene glycol dimethacrylate and tetraethylene glycol dimethyl methacrylate. Mono- or diacrylate and methacrylate of ethylene glycol or polyethylene glycol such as acrylate; mono- or diacrylate and methacrylate of propylene glycol or polypropylene glycol; mono-, di- or tri-acrylate of glycerin and Methacrylate; cyclohexane diacrylate and dimethacrylate; 1,4-butanediol diacrylate and dimethacrylate; 1,6-hexanediol diacrylate and dimethyl acrylate Acrylate; diacrylate and dimethacrylate of neopentyl glycol; mono or diacrylate and methacrylate of bisphenol A; benzene trimethacrylate, isopropyl acrylate and methacrylic acid Isopropyl ester; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and methacrylate; glycerol di- or triacrylate and methacrylate; Di-, tri- or tetra-acrylate and methacrylate of pentaerythritol; and compounds such as ethylene oxide or propylene oxide adducts of these compounds.

When the photosensitive resin composition contains other photopolymerizable unsaturated monomers, the blending amount is preferably 50 parts by mass or less, more preferably 30 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1) Parts by mass or less, particularly preferably 10 parts by mass or less. When the photosensitive resin composition contains other photopolymerizable unsaturated monomers, the blending amount may be more than the blending amount of the above-mentioned (G) polymerizable unsaturated monomer having 3 or more polymerizable functional groups, also It may be less than the compounding amount of the polymerizable unsaturated monomer having 3 or more polymerizable functional groups in the above (G), and may be the same. The lower limit of the blending amount of other photopolymerizable unsaturated monomers may be, for example, 1 part by mass or more, or more than 1 part by mass relative to 100 parts by mass of the (A, A1) polyimide precursor.

In one embodiment, in order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate, the photosensitive resin composition may optionally contain an adhesive auxiliary agent. Examples of the adhesive aid include: γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyl dimethoxysilane, and γ-glycidol Oxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxy Propyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropyl silane, diethoxy-3-glycidoxypropylmethyl silane, N-(3-diethoxy Methylsilylpropyl) succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N -[3-Triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide) )-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl trimethoxysilane and other silane coupling agents (wherein, the above (F) Except for components), and aluminum-based adhesives such as tris(ethyl acetone acetate) aluminum, tris (acetone acetone) aluminum, and ethyl aluminum diisopropyl acetyl acetate.

Among these adhesion assistants, it is more preferable to use a silane coupling agent (except for the above-mentioned (F) component) in terms of adhesion. The compounding amount of the auxiliary agent is preferably in the range of 0.5 parts by mass to 25 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1).

Thermal polymerization inhibitor In order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition when stored in a state containing a solvent, especially a solution containing the (D2) solvent, the negative photosensitive resin composition of the present embodiment may optionally contain Thermal polymerization inhibitor. As thermal polymerization inhibitors, you can use: hydroquinone, N-nitrosodiphenylamine, p-tertiary butylcatechol, phenothionine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1 ,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N- Phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc.

The blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1).

{式中，R₁ 、R₂ 、R₃ 及R₄ 係碳數1～40之1價有機基}(I) Compound having a hydroxyl group and a polymerizable unsaturated bond (I) a compound having a hydroxyl group and a polymerizable unsaturated bond (hereinafter also simply referred to as "(I) compound") in one embodiment will be described. (I) The compound has at least one hydroxyl group and at least one polymerizable unsaturated bond in the molecule. The polymerizable unsaturated bond is not particularly limited, as long as it is a functional group capable of radical polymerization, and examples thereof include acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, and vinyl group. , And allyl group, etc., preferably acryloxy or methacryloxy (referred to as "(meth)acryloxy" in the present specification). As the (I) compound having a (meth)acryloyloxy group as a polymerizable unsaturated bond, it can also be acrylic acid or methacryloyl group (also referred to as "(meth)acrylic acid" in this case) and epoxy The reactant of the resin, or the reactant of the ring-opening body of (meth)acrylic acid and epoxy resin. Among them, from the viewpoints of chemical resistance and thermophysical properties, a reaction product of (meth)acrylic acid and epoxy resin represented by any of the following general formulas, or (meth)acrylic acid and cyclic The reactant of the ring-opening body of the oxygen resin. [化45]

{Where R ₁ , R ₂ , R ₃ and R ₄ are monovalent organic groups with 1 to 40 carbons}

{式中，R₂ 、R₃ 係碳數1～40之2價有機基}。(I) The compound may have one, two or more, or three or more polymerizable unsaturated bonds in the same molecule. When there are two polymerizable unsaturated bonds, the compounds represented by the following general formulas can be cited: [化46]

{In the formula, R ₂ and R ₃ are divalent organic groups with 1 to 40 carbon atoms}.

[化48]

[化49]

[化50]

More specifically, as the (I) compound having two polymerizable unsaturated bonds, the following compound groups can be cited, but are not limited to them. [Chemical 47]

[化48]

[化49]

[化50]

{式中，R₁ 、R₂ 、R₃ 及R₄ 分別獨立地為碳數1～40之2價有機基}。其等之中，較佳為下述通式所表示之化合物： [化52]

{式中，R₆ 為碳數1～40之2價有機基}。The (I) compound having two or more polymerizable unsaturated bonds can be produced by reacting (meth)acrylic acid with a bifunctional or higher epoxy resin. In this case, sometimes a compound having an oxocyclopropyl group having more than one function in the molecule is produced as a reaction impurity. Examples of reaction impurities include compounds represented by the following general formula: [化51]

{In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a divalent organic group having 1 to 40 carbon atoms}. Among them, preferred are compounds represented by the following general formula: [化52]

{In the formula, R ₆ is a divalent organic group with 1 to 40 carbon atoms}.

As the (I) compound, when there is one polymerizable unsaturated bond, the following compound groups can be cited, but are not limited to them: [化53]

(I) Preparation method of compound with hydroxyl group and polymerizable unsaturated bond (I) The method for producing the compound is not particularly limited, as long as a compound having at least one hydroxyl group and at least one polymerizable unsaturated bond in the molecule can be obtained. In order to adjust the amount of (J1) free chlorine and/or (J2) covalently bonded chlorine to a specific amount, the (I) compound is preferably a compound derived from an epoxy resin. For example, the compound (I) can be produced by reacting an epoxy resin or its ring opener with a compound having a polymerizable unsaturated bond. It is preferable to add a basic catalyst and a polymerization inhibitor to the epoxy resin or its ring-opened body to obtain a solution, and to add methacrylic acid or acrylic acid to the solution and react, thereby also producing the (I) compound. The reaction can be continued at 100°C, for example, until the acid value becomes a certain value or less. After synthesis, the mixture with the anion exchange resin is stirred for 1 day and filtered to obtain (I) compound. As the anion exchange resin, for example, IRA96SB can be used.

As the epoxy resin used in the synthesis reaction of the compound (I), the structure represented by the following general formula may be mentioned, but it is not limited to these and the like: [化54]

{式中，R₁ 及R₂ 分別獨立地為碳數1～40之1價有機基}。As the ring-opening body of the epoxy resin used in the synthesis reaction of the compound (I), it is preferably converted into a compound having a structure represented by the following general formula for ring opening of an epoxy group: [化55]

{In the formula, R ₁ and R ₂ are each independently a monovalent organic group having 1 to 40 carbon atoms}.

The sensitizer resin composition of one embodiment contains the above-mentioned (I) compound, thereby providing a resin film that maintains storage stability, has a high glass transition temperature and a high thermal weight loss temperature, and has excellent chemical resistance. Although the reason for the glass transition temperature rise is not bound by theory, it is believed that the reason is as follows: the polymerizable unsaturated bond remaining unpolymerized during exposure progresses with the addition reaction of the hydroxyl group during high-temperature hardening, thereby obtaining a more usual content The polymerizable unsaturated bond compound cross-links the cured film with a higher density, thereby hindering the movement of the polymer constituting the resin. Furthermore, when the polymerizable unsaturated bond is a (meth)acryloyl group, the Michael addition reaction proceeds. Regarding the reasons for the improvement in chemical resistance, it is considered that the reasons are as follows: similarly, the cross-linking density is higher and the solubility in chemicals is reduced, and (J1) free chlorine and/or (J2) covalently bonded chlorine The amount is within a specific range, so it inhibits the formation of ion pairs with the medicinal solution that has a dissolution-promoting effect, thereby improving chemical resistance. As the reason for the increase in the thermoweight loss temperature, it is believed that the reason is as follows: the addition reaction of polymerizable unsaturated bonds and hydroxyl groups with the side chain of the polyimide precursor will cause the thermoweight loss temperature to decrease, especially during low-temperature hardening. Even when it rises above the curing temperature, the components derived from the side chains of the polyimide precursor remain unvolatile and remain, thereby preventing weight loss due to heating.

When a bifunctional or more epoxy resin is used in the synthesis of the compound (I), the compound (I) may have an unreacted epoxy group. In this case, the anionic polymerization proceeds with the hydroxyl group as the starting species at the time of thermal curing, so that the crosslink density further increases.

(I) The compounding amount of the compound is 1 part by mass to 60 parts by mass relative to 100 parts by mass of the polyimide precursor (A, A1). From the viewpoint of storage stability, it is preferably 1 part by mass to 30 From the viewpoint of resolution, parts by mass are more preferably 4 parts by mass to 20 parts by mass.

(J1) Free chlorine and/or (J2) Covalently bonded chlorine The photosensitive resin composition of one embodiment is contained in the form of free chlorine and/or covalently bonded chlorine. Free chlorine refers to anionized chlorine, and covalently bonded chlorine refers to the chlorine that forms a covalent bond and exists in the molecule.

In one embodiment, the amount of (J1) free chlorine is 0.0001-10 ppm based on the total mass of the photosensitive resin composition, preferably 0.0001-5 ppm, more preferably 0.0001-2.0 ppm, More preferably, it is 0.0001 to 0.5 ppm. In another embodiment, the photosensitive resin composition is spin-coated on the base plate so that the thickness of the cured resin film becomes about 10 μm, and it is heated on a hot plate at 110°C for 180 seconds. When cured, the amount of (J1) free chlorine contained in the obtained coating film is based on the total mass of the coating film, which is 0.0001-15 ppm, preferably 0.0001-10 ppm, more preferably 0.0001-5 ppm, More preferably, it is 0.0001 to 0.8 ppm. In another embodiment, when the photosensitive resin composition is adjusted and left to stand for 3 days at 23°C±0.5°C and a relative humidity of 50%±10%, the total amount of chlorine in the photosensitive resin composition (free chlorine and The total amount of covalently bonded chlorine) is 0.0001 to 600 ppm based on the total mass of the photosensitive resin composition, preferably 0.0001 to 420 ppm, more preferably 0.0001 to 250 ppm, and still more preferably 0.0001 to 40 ppm.

The supply source of chlorine is not limited. For example, the amount of chlorine can be adjusted to the above range by including a compound capable of generating free chlorine and/or a compound having covalently bonded chlorine in the photosensitive resin composition. Generally speaking, epoxy resins contain a large amount of chlorine derived from epichlorohydrin as its raw material and in the form of free chlorine and/or covalently bonded chlorine in the resin. Therefore, when the compound (I) is a compound derived from an epoxy resin, the compound (I) contains chlorine. As a result, the photosensitive resin composition also contains chlorine, so it is easier to adjust the amount of chlorine Within the above range. Therefore, when the compound (I) derived from epoxy resin was used in this way, the amount of chlorine would be far more than the above-mentioned amount. Since the existence of this kind of chlorine was previously allowed, the industry did not pay attention to the amount of chlorine. However, the inventors have discovered that in the preferred embodiment of the fourth aspect of the invention, when the epoxy resin-derived compound (I) is used, it is preferable to remove the chlorine present in the compound to Properly control the amount of chlorine.

The method for removing the chlorine present in the (I) compound derived from the epoxy resin is not particularly limited. For example, the chlorine can be removed by stirring the compound (I) in the form of a mixed phase with the anion exchange resin. As an anion exchange resin used for chlorine removal, IRA96SB can be mentioned, but it is not limited to this.

(K) Urea compounds The (K) urea compound used in this embodiment is not limited as long as it has a urea bond in the molecular structure. From the viewpoint of chemical resistance and the viewpoint that it is easy to adjust the peak intensity after contact/peak intensity before contact to the range of this embodiment, the (K) urea compound preferably has the above-mentioned general formula (3 ) Or (4) urea compound.

_{R 9} and R ₁₀ in the formula (3) may be bonded to each other to have a cyclic structure. From the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. R ₉ and R ₁₀ are bonded to each other and have a cyclic structure, which will cause the urea group to lose freedom of the bonding angle, and it is difficult to form a strong hydrogen bond.

_{R 11} and R ₁₂ in the formula (4) may be bonded to each other to have a cyclic structure. From the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. R ₁₁ and R ₁₂ are bonded to each other to have a cyclic structure, which will cause the urea group to lose freedom of the bonding angle, and it is difficult to form a strong hydrogen bond.

In this embodiment, the (K) urea compound preferably further has at least one functional group selected from the group consisting of (meth)acrylic groups, hydroxyl groups, and amino groups.

In this embodiment, the molecular weight of the (K) urea compound is preferably 150 g/mol or more, and more preferably 250 g/mol or more. If the molecular weight of the urea compound is 250 g/mol or more, the urea compound is not easy to volatilize during the heating and curing process, and the effect of promoting the imidization becomes higher.

(K) The number of urea groups in the molecule of the urea compound is preferably 1 or 2. If the number of urea groups in the molecule is less than 3, the interaction of the urea compounds with each other is small, the solubility is improved, and the filterability of the resin composition becomes good.

(K) The molecular weight (MW/number of urea groups) of each urea group of the urea compound is preferably 150 g/mol or more, and more preferably 200 g/mol or more. If the molecular weight of each urea group is 200 g/mol or more, the interaction of the urea compounds with each other is small, the solubility is improved, and the filterability of the resin composition becomes good.

By containing the (K) urea compound of this embodiment, it is easy to adjust the peak intensity before and after the contact of the standard TMAH solution to the range of this embodiment. As a result, the wettability after alkaline solution treatment tends to improve. The reason is not clear, but the inventors of the present invention believe that it is as follows. First, when the photosensitive resin composition containing the polyimide precursor is usually heated and cyclized at a relatively low temperature of, for example, 170°C, there is a conversion of the polyimide precursor to the polyimide and Trend of inadequacy. On the other hand, it is considered that since the photosensitive resin composition of the present embodiment contains the (K) urea compound, a part of the (K) urea compound is thermally decomposed to generate amines, etc., which promote the polyimide precursor The substance is converted to polyimide. In addition, it is considered that in a preferred embodiment of the fifth aspect of the invention, since the (K)urea compound further has a (meth)acryloyl group, it is especially used when the photosensitive resin composition is negative By light irradiation, using compound (C1) as an initiator, the (meth)acrylic acid group of (K) urea reacts with the side chain part of the polyimide precursor (A, A1) to be cross-linked. As a result, the (K) urea compound is more likely to exist in the vicinity of the (A, A1) polyimide precursor, so that the conversion efficiency can be drastically improved. Thereby, the dissolution rate of the cured film when in contact with the alkaline solution is suppressed, and the cured film remains sufficiently even after contact with the alkaline solution. Then, (K) the urea compound is thought to strongly hydrogen bond with functional groups such as imine groups. It is considered that by this, even when a part of the imino group is ring-opened by the alkaline solution, the film remains undissolved in the alkaline solution due to hydrogen bonding. It is considered that by this, the imine ring opens on the surface of the film and becomes a state where the functional group with higher hydrophilicity is exposed, and the wettability is improved.

In the present embodiment, when the (K)urea compound further has a (meth)acryloyl group, the (meth)acryloyl group equivalent of the (K)urea compound is preferably 150 to 400 g/mol. By making the (meth)acrylic acid equivalent of the (K)urea compound 150 g/mol or more, the chemical resistance of the negative photosensitive resin composition tends to become good. By making (K)urea The (meth)acrylic acid equivalent of the compound is 400 g/mol or less, and the developability tends to become better. (K) The lower limit of the (meth)acrylic acid equivalent of the urea compound is more preferably 200 g/mol or more, 210 g/mol or more, 220 g/mol or more, 230 g/mol or more, and more preferably 240 g/mol or more and 250 g/mol or more, and the lower limit is more preferably 350 g/mol or less, 330 g/mol or less, and still more preferably 300 g/mol or less. (K) The (meth)acrylic acid equivalent of the urea compound is more preferably 210 to 400 g/mol, and particularly preferably 220 to 400 g/mol.

(K) The manufacturing method of a urea compound is not specifically limited, For example, it can obtain by making an isocyanate compound and an amine-containing compound react. When the above-mentioned amine-containing compound contains functional groups such as a hydroxyl group that can react with isocyanate, it may also include a compound obtained by reacting a part of the isocyanate compound with a functional group such as a hydroxyl group.

(K) The urea compound in this embodiment may be used individually by 1 type, or 2 or more types may be mixed and used for it.

(K) The compounding amount of the urea compound is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the polyimide precursor (A, A1). The compounding amount of the urea compound is 1 part by mass or more from the viewpoint of chemical resistance, and 50 parts by mass or less from the viewpoint of film physical properties and photopatterning.

<Method of manufacturing hardened relief pattern and semiconductor device> The manufacturing method of the hardened embossed pattern of this embodiment includes the following steps: (1) The above-mentioned negative photosensitive resin composition of this embodiment is coated on a substrate, and a photosensitive resin layer is formed on the above-mentioned substrate; (2) Expose the above-mentioned photosensitive resin layer; (3) Developing the above-mentioned photosensitive resin layer after exposure to form a relief pattern; and (4) The above-mentioned embossed pattern is heated to form a hardened embossed pattern.

The manufacturing method of the hardened relief pattern may further include the following steps as required: (5) Bring the above-mentioned hardened relief pattern into contact with an alkaline solution; and (6) Heat treatment of the above-mentioned hardened relief pattern in contact with the above-mentioned alkaline solution.

(1) Steps for forming photosensitive resin layer In this step, the negative photosensitive resin composition of this embodiment is coated on a substrate, and then dried as necessary to form a photosensitive resin layer. As the coating method, the methods previously used for coating the photosensitive resin composition can be used, such as the use of a spin coater, bar coater, knife coater, curtain coater, and screen printer. Such as coating method, and spray coating method with spraying machine.

If necessary, the coating film containing the photosensitive resin composition may be dried. As the drying method, air drying, heating drying using an oven or hot plate, vacuum drying, etc. can be used. Specifically, in the case of air drying or heat drying, it can be dried under the conditions of 20°C to 140°C for 1 minute to 1 hour. In this way, a photosensitive resin layer can be formed on the substrate.

(2) Exposure step In this step, the photosensitive resin layer formed in the above is exposed by an ultraviolet light source or the like. As the exposure method, exposure devices such as a contact aligner, a mirror projection exposure machine, and a stepper can be used. Exposure can be performed through a patterned photomask or grating, or directly.

Thereafter, for the purpose of improving the light sensitivity, post-exposure bake (PEB) and/or pre-development bake under any combination of temperature and time may be implemented as needed. Regarding the range of the baking conditions, the temperature is preferably from 40°C to 120°C and the time is from 10 seconds to 240 seconds.

(3) Relief pattern formation step In this step, the unexposed part of the photosensitive resin layer after exposure is developed and removed from the substrate, thereby leaving the embossed pattern on the substrate. As a development method for developing the photosensitive resin layer after exposure (irradiation), it can be selected from the previously known development methods of photoresist, such as rotary spray method, liquid coating method, dipping method with ultrasonic treatment, etc. Use any method. Moreover, after development, for the purpose of adjusting the shape of the embossed pattern, etc., post-development baking under any combination of temperature and time may be implemented as needed.

As the developer used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, gamma -Butyrolactone, α-acetyl-γ-butyrolactone, etc. As a poor solvent, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferable, for example. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Moreover, each solvent can also be used in combination of 2 or more types, for example in combination of several types.

(4) Hardening relief pattern formation step In this step, the embossed pattern obtained by the above development is heated to dilute the photosensitive components, and the (A, A1) polyimide precursor is imidized, thereby converting it into a polyimide Hardened embossed pattern of amine. As the method of heating and hardening, for example, various methods can be selected, such as a method using a hot plate, a method using an oven, and a method using a temperature-rising oven with a set temperature control program. The heat treatment can be performed at 160°C to 350°C, or 170°C to 400°C, preferably at 160°C to 200°C or 170°C to 300°C, and more preferably at 160°C to 180°C or 170°C to 250°C. It is further preferably carried out at 160°C to 170°C or 170°C to 200°C, for example, under the conditions of 30 minutes to 5 hours. As the ambient gas during heating and curing, air can be used, or inert gases such as nitrogen and argon can also be used.

(5) Alkaline solution contact step for hardening embossed patterns In this step, by contacting the hardened embossed pattern obtained in (4) the hardened embossed pattern forming step with an alkaline solution, the in-plane uniformity of the hardened embossed pattern containing polyimide can be improved. The alkali source of the alkaline solution is not limited as long as the in-plane uniformity can be improved. For example, tetramethylammonium hydroxide pentahydrate (TMAH) can be mentioned. As the solvent of the alkaline solution, for example, dimethyl sulfoxide (DMSO) can be cited. Typically, a DMSO solution of TMAH can be used, and more specifically, a DMSO solvent of 2.38% by mass of TMAH can be used. The alkaline solution may also contain amines such as monoethanolamine, or a solvent as other components. As an alkaline solution, a stripping solution for stripping photoresist or dry film photoresist can also be used. The contact with the alkaline solution can be carried out at room temperature to 100°C for 5 minutes to 120 minutes, for example. When in contact with alkaline solution, the solution can also be stirred. The cured film after contact with alkaline solution can also be washed with organic solvent or water and then dried. The temperature during drying is preferably 100°C or lower. As the ambient gas during drying, air can be used, or inert gases such as nitrogen and argon can also be used.

The alkaline solution contacting step can be performed just after the hardened relief pattern is formed, or it can be performed in the following state, that is, after the hardened relief pattern is formed, Ti/Cu sputtering is performed to form the photoresist pattern, and the photoresist pattern is formed by plating. And the state with Cu wiring is formed. In this case, the alkaline solution peels off the photoresist, and then penetrates from the edge of the wafer or the sputtering pinhole, so it can play a role in hardening the embossed pattern. That is, the contact step with the alkaline solution may be a photoresist stripping step.

(6) Reheat treatment of hardened embossed pattern after contact with alkaline solution In this step, the hardened relief pattern after contact with the alkaline solution is reheated. This step can be performed immediately after the alkaline solution contacting step, or after the alkaline solution contacting step, the upper relief pattern is formed on the hardened relief pattern and then performed later. That is, the step of reheating the hardened embossed pattern after contact with the alkaline solution can be performed simultaneously with the heating of the embossed pattern of the upper layer after forming two or more multilayer interlayer insulating films. As the method of heating treatment, for example, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-rising oven with a temperature control program can be selected. The heat treatment can be performed under the conditions of 160°C to 350°C for 30 minutes to 5 hours, for example. The temperature of the heat treatment is preferably 160°C to 200°C, more preferably 160°C to 180°C, and still more preferably 160°C to 170°C. As the ambient gas during heating and curing, air can also be used, and inert gases such as nitrogen and argon can also be used.

In the manufacturing method of the hardened embossed pattern of this embodiment, it is preferable that the hardened embossed pattern obtained in the above step (4) and the hardened embossed pattern obtained in the above step (6) be 1500 cm ^-1 the IR peak intensity near 1778 cm ^-1 cured relief pattern of the IR peak intensity in the vicinity of 1778 cm ^-1 when the normalized IR peak intensity higher than the above-described step (5) obtained in the. In the above step (5), ^{the IR peak intensity around 1778 cm -1 of} the hardened embossed pattern is temporarily reduced, thereby imparting wettability to the hardened film, thereby obtaining a hardened embossed pattern with higher in-plane uniformity .

<Cured film> The cured film of this embodiment is characterized in that when it is in contact with a DMSO solution of TMAH at a temperature of 50°C and 2.38% by mass (hereinafter also referred to as "standard TMAH solution") for 10 minutes, it uses an IR of ^{1500 cm -1 The IR peak intensity around 1778 cm -1} when the peak intensity is normalized falls within the range of the following formula (1) before and after the contact. 0.1≦(peak intensity after contact/peak intensity before contact)≦0.8 (1)

When the IR peak intensity of the cured film is within the above range, the hydrophilicity of the cured film is increased, and the cured film has wettability suitable for further coating the photosensitive resin composition on the cured film. From the viewpoint of chemical resistance, the value of peak intensity after contact/peak intensity before contact is preferably 0.1 or more, more preferably 0.3 or more, and still more preferably 0.5 or more. The cured film whose peak strength after contact/peak strength before contact is less than 0.1 has poor chemical resistance. From the viewpoint of wettability, the value of peak intensity after contact/peak intensity before contact is preferably 0.8 or less, more preferably 0.7 or less, and still more preferably 0.6 or less.

The amount of change in the film thickness before and after the contact is preferably 1 nm or more and 1000 nm or less. If the solubility to the alkaline solution is high, the pattern will be degraded (cracking, pattern shape collapse), so the thickness change of the cured film when in contact with the standard TMAH solution is more preferably 600 nm or less, and more preferably Below 300 nm. The thickness change of the cured film is measured by adjusting the thickness of the cured film before contact to approximately 3 μm.

From the viewpoint of deaeration or curing shrinkage in the step in the case of forming a multilayer body, the imidization rate of the cured film before contact with the standard TMAH solution is preferably 70% or more and 100% or less. When the imidization rate is less than 70%, degassing or hardening shrinkage becomes a problem in the step after the chemical liquid is contacted. The imidization rate is more preferably 80% or more, and still more preferably 90% or more.

{通式(10)中，X¹ 及Y¹ 分別與通式(1)中之X₁ 及Y₁ 相同，並且m為正之整數}<Polyimine> The structure of the polyimide contained in the hardened relief pattern formed from the polyimide precursor composition is represented by the following general formula (10). [化56]

{In the general formula (10), X and Y ¹ are (1) the same as X ¹ and Y ₁ in the general formula _1, and m is a positive integer} of

The preferable X ₁ and Y ₁ in the general formula (1) are also preferable in the polyimide of the general formula (10) for the same reason. The number m of repeating units of the general formula (10) may also be an integer of 2 to 150. In addition, the production method of polyimide including the step of converting the (A, A1) polyimide precursor contained in the negative photosensitive resin composition described above into polyimide is also the subject of the present invention In the same state.

＜Semiconductor device＞ In this embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned manufacturing method of a cured relief pattern is also provided. Therefore, it is possible to provide a semiconductor device having a substrate as a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-mentioned manufacturing method of the cured relief pattern. In addition, the present invention can also be applied to a method of manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the method of manufacturing the above-mentioned hardened relief pattern as part of the steps. The semiconductor device of this embodiment can be used as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip-chip devices, or having convexities by forming a hardened embossed pattern formed by the above-mentioned hardened embossed pattern manufacturing method. Block structure semiconductor device protection film, etc., and combined with the known manufacturing method of semiconductor device to manufacture.

＜Display device＞ In this embodiment, there is provided a display device including a display element and a cured film disposed on the upper portion of the display element, and the cured film is the above-mentioned cured embossed pattern. Here, the hardened embossed pattern may be directly connected to the display element to be laminated, or another layer may be sandwiched therebetween to be laminated. For example, the cured film includes: surface protection films, insulating films, and planarizing films of thin film transistor (TFT) liquid crystal display elements and color filter elements, and those used for multi-domain vertical alignment (MVA) type liquid crystal display devices Protrusions and partition walls for the cathode of organic electroluminescence (EL) devices.

The photosensitive resin composition of the present embodiment is preferably a photosensitive resin composition for forming an insulating member or forming an interlayer insulating film.

The photosensitive resin composition or negative photosensitive resin composition of this embodiment is not only applied to the above-mentioned semiconductor device, but also can be used for interlayer insulation of multilayer circuits, cover coating of flexible copper foil, and solder mask. , And liquid crystal alignment film and other uses. [Example]

Hereinafter, the present embodiment will be specifically described with examples, but the present embodiment is not limited to this. In the examples, comparative examples, and production examples, the physical properties of the polyimide precursor, polymer, photosensitive resin composition, or negative photosensitive resin composition were measured and evaluated according to the following methods.

<The first to third aspects: measurement and evaluation methods> (1) Weight average molecular weight, number average molecular weight, and degree of dispersion The weight average molecular weight (Mw) and number average molecular weight (Mn) of each resin are measured under the following conditions using gel permeation chromatography (standard polystyrene conversion). Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ String: Shodex KD-806M manufactured by Showa Denko Co., Ltd., 2 in series, or Shodex 805M/806M series manufactured by Showa Denko Co., Ltd. Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd. Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL/min

For each resin, the weight average molecular weight (Mw)/number average molecular weight (Mn) is calculated as necessary to calculate the degree of dispersion. Here, when two types of polymers described in the examples and comparative examples are mixed, the weight average molecular weight (Mw) and number average molecular weight (Mn ) While calculating the degree of dispersion (Mw/Mn).

(2) I-ray absorbance measurement (A, A1) The i-ray absorbance of the polyimide precursor is measured as follows: adjust 0.1 wt% NMP solution (the NMP solution containing 0.1 wt% (A, A1) polyimide precursor), and fill After being placed in a 1 cm quartz cell, use the UV-1800 device manufactured by Shimadzu Corporation to measure at a medium-speed scanning speed and a sampling interval of 0.5 nm. Here, when two types of polymers described in the Examples and Comparative Examples are mixed, the i-ray absorbance is measured for the mixed polymer obtained by mixing in each mass ratio.

(3) Evaluation of cracks when forming a 2-layer polyimide film on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm), using a sputtering device (L-440S-FHL) Type, CANON ANELVA Co., Ltd.) Sputter Ti with a thickness of 200 nm and Cu with a thickness of 400 nm in sequence. Then, using a coating and developing machine (Model D-Spin60A, manufactured by SOKUDO), the negative photosensitive resin composition prepared by the following method was spin-coated on the wafer, and a hot plate was used at 110°C. Perform pre-baking for 180 seconds to form a coating film about 7 μm thick. Using a mask with a test pattern, the coating film was irradiated with energy of ^{100 to 500 mJ/cm 2 by Prisma GHI (manufactured by Ultratech).} Then, cyclopentanone was used as a developer, and the coating film was spray-developed using a coating developer (Model D-Spin60A, manufactured by SOKUDO), and washed with propylene glycol methyl ether acetate, thereby obtaining the Cu on Embossed pattern. Using a temperature-temperature program curing furnace (VF-2000, manufactured by Koyo Lindberg), under a nitrogen atmosphere and at the curing temperature described in the following table for 2 hours, the wafer with the embossed pattern formed on the Cu was processed Heat treatment to obtain a hardened relief pattern containing resin with a thickness of about 4-5 μm on Cu. Then, for the embossed pattern after the heat treatment, coating, exposure, and curing are performed again under the same conditions. For the cured polyimide film, the number of cracks per wafer is evaluated as × (bad), and the number of cracks per wafer is evaluated as △ (allowed). , And those without cracks were evaluated as ○ (good).

(4) Adhesion test with sealing material As an epoxy-based sealing material, prepare R4000 series manufactured by Nagase Chemtex. The sealing material is spin-coated on a silicon wafer sputtered with aluminum so that the thickness becomes about 150 μm, and the epoxy-based sealing material is cured by thermal curing at 130°C. The photosensitive resin composition produced in each example and each comparative example was applied on the epoxy-based cured film so that the final film thickness became 10 μm. Using an alignment machine (PLA-501F, manufactured by Canon), the entire surface of the coated photosensitive resin composition was exposed with ghi rays ^{with an exposure amount of 600 mJ/cm 2.} Thereafter, the exposed photosensitive resin composition was thermally cured at 180°C for 2 hours to form a first cured film with a thickness of 10 μm.

The photosensitive resin composition used in the formation of the first layer of the cured film is coated on the above-mentioned first layer of cured film, the entire surface is exposed under the same conditions as when the first layer of cured film is made, and then thermally cured, and A second hardened film with a thickness of 10 μm is produced. A pin was set on the sample made in the deterioration test of the sealing material, and an adhesion test was performed using a coiling tester (manufactured by Quad Group, Sebastian Type 5). That is, the adhesive strength of the epoxy-based sealing material and the cured embossed pattern produced from the photosensitive resin composition produced in each example and each comparative example was measured, and evaluated based on the following criteria. Evaluation: Adhesion strength above 70 MPa Adhesive force A Then the strength is above 50 MPa ~ less than 70 MPa Adhesion B Then the strength is above 30 MPa to less than 50 MPa Adhesion C Then the strength did not reach 30 MPa Adhesion force D

(5) Elongation after HTS (High Temperature Storage Test: Reliability Test) On a 6-inch silicon wafer pre-sputtered with aluminum, the negative photosensitive resin composition was coated under the same conditions as the above (3) crack evaluation, and then the HTS test (150°C, 168 hours, in the air). After the test, for the wafer, use a wafer dicing machine (manufactured by DISCO Co., Ltd., DAD 3350) to cut a 3 mm wide slit on the polyimide resin film of the wafer, and then immerse it in a dilute hydrochloric acid aqueous solution One night, the resin film is peeled off and dried. Cut it to a length of 50 mm as a sample. For the above-mentioned samples, the elongation (%) was measured at a test speed of 40 mm/min and an initial load of 0.5 fs using TENSILON (UTM-II-20 manufactured by Orientec).

(6) Storage stability test With respect to the photosensitive resin composition produced in the following examples, the viscosity was measured immediately after the preparation and after being allowed to stand at 23°C for 1 month, and the rate of change was calculated. Change rate (%) = Viscosity after 1 month standing at 23℃×100/Viscosity just after conditioning Furthermore, the viscosity is measured by the following method. Using an E-type viscometer (RE-80H, manufactured by Toki Sangyo Co., Ltd.), the viscosity of the photosensitive resin composition was measured under the conditions of a measurement temperature of 23°C, a rotation speed of 1-10 rpm, and a measurement time of 5 minutes. In addition, JS2000 (manufactured by NIPPON GREASE) was used as a standard solution for viscometer calibration. A rate of change of 10% or less is evaluated as A, a rate of change of more than 10% and 20% or less is evaluated as B, and a rate of change of more than 20% is evaluated as C.

＜The first aspect (I)＞

Production Example I-1: Synthesis of polymer A-1 as the precursor of (A) polyimine Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a separable flask with a capacity of 2 L, and add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and γ- 400 mL of butyrolactone was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the exotherm caused by the reaction, the reaction mixture was left to cool to room temperature and kept for 16 hours. Then, while cooling in an ice bath, the solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was stirred while being added to the reaction mixture over 40 minutes. Then, while stirring 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone, the mixture was added for 60 minutes. Furthermore, after continuing to stir at room temperature for 2 hours, 30 mL of ethanol was added and stirring was continued for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polymer A-1). The molecular weight of the polymer (A-1) was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 20,000.

Production Example I-2: Synthesis of polymer A-2 as the precursor of (A) polyimine Use 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example I-1, except that The reaction was carried out in the same manner as the method described in the above-mentioned Production Example I-1 to obtain a polymer (A-2). The molecular weight of the polymer (A-2) was measured by gel permeation chromatography (in terms of standard polystyrene). As a result, the weight average molecular weight (Mw) was 21,000.

Production Example I-3: Production method of MOI-D (Compound B-1) Add 55.1 g (0.25 mol) of diethylene glycol bis(3-aminopropyl) ether into a separable flask with a capacity of 500 mL, add 150 mL of tetrahydrofuran, and stir at room temperature. Then, the solution obtained by adding 150 mL of tetrahydrofuran to 77.6 g (0.50 mol) of 2-methacryloxyethyl isocyanate (product of Showa Denko Co., Ltd., product name: Karenz MOI) was added to 150 mL of tetrahydrofuran under ice cooling for 30 minutes Add dropwise to the above flask and keep stirring at room temperature for 5 hours. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound B-1.

Production Example I-4: Production method of MOI-AEE (Compound B-7) In the above production example I-3, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 26.3 g (0.25 mol) of 2-(2-aminoethoxy)ethanol, and the isocyanate 2-methacrylic acid oxyethyl ester (product of Showa Denko Corporation, product name: Karenz MOI) 77.6 g was replaced with 38.8 g (0.25 mol), except that it was synthesized by the same method as in Production Example I-3 , And obtain compound B-7.

Manufacturing example I-5 MOI-DOA manufacturing method (compound B-8) In the above production example I-3, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 60.4 g (0.25 mol) of di-n-octylamine, and 2-methylpropene isocyanate Except that 77.6 g of oxyethyl ester (product of Showa Denko Corporation, product name: Karenz MOI) was replaced with 38.8 g (0.25 mol), the compound was synthesized in the same manner as in Production Example I-3 to obtain compound B- 8.

Production Example I-6 (Compound B-11) 2.10 g (0.020 mol) of diethanolamine was added to a three-necked flask with a capacity of 100 mL, 5.6 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. Then, the solution obtained by adding 5.6 g of tetrahydrofuran to 2.67 g (0.021 mol) of hexyl isocyanate was added dropwise to the flask over 15 minutes under ice-cooling, and stirring was continued for 4 hours at room temperature. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound B-11.

<Example I-1> Using polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) Polyimide precursor polymer A-1: 100 g, (B) Compound B-1 of Production Example I-3: 8 g, (C) photopolymerization initiator The ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (OXE-02, equivalent In photopolymerization initiator C-1): 3 g was dissolved in 3-methoxy-N,N-dimethylpropanamide: 150 g. Furthermore, a small amount of 3-methoxy-N,N-dimethylpropanamide was added to adjust the viscosity of the obtained solution to about 30 poises to prepare a negative photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 1.

<Examples I-2 to I-7, Comparative Example I-1> Except for preparing at the compounding ratio shown in Table 1, a negative photosensitive resin composition was prepared in the same manner as in Example I-1, and evaluated according to the above-mentioned method. The results are shown in Table 1.

[化58]

The compounds (B-1, 7, 8, 11), photopolymerization initiator (C-1), and solvent (D-1 to D-3) described in Table 1 are the following compounds, respectively. [化57]

[化58]

C-1: Ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (trade name : IRGACURE OXE-02(OXE-02)) D-1: 3-Methoxy-N,N-dimethylpropanamide (manufactured by KJ Chemicals: brand name KJCMPA-100) D-2: 3-Butoxy-N,N-dimethylpropanamide (manufactured by KJ Chemicals: brand name KJCBPA-100) D-3: N-methyl-2-pyrrolidone (NMP)

[Table 1] Example Comparative example I-1 I-2 I-3 I-4 I-5 I-6 I-7 I-1 polymer* A-1 100 100 A-2 100 100 100 100 100 100 Compound* B-1 8 8 8 8 B-7 8 B-8 8 B-11 8 Photopolymerization initiator* C-1 3 3 3 3 3 3 3 3 Solvent* D-1 150 150 150 150 150 D-2 150 150 D-3 150 Hardening temperature (℃) 180 180 180 180 180 180 180 180 Adhesion test with sealing material B B B B A B A D Crack test △ △ 〇 〇 〇 〇 〇 X Elongation after HTS (%) 30 20 40 32 42 36 42 12 *Unit: g

＜The second aspect (II)＞

Production Example II-1: Synthesis of polymer A-1 as the precursor of (A) polyimine Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a separable flask with a capacity of 2 L, and add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and γ- 400 mL of butyrolactone was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the exotherm caused by the reaction, the reaction mixture was left to cool to room temperature and allowed to stand for 16 hours. Then, under ice-cooling, the solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was stirred while being added to the reaction mixture over 40 minutes Then, while stirring 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone, the mixture was added for 60 minutes. After further stirring for 2 hours at room temperature, 30 mL of ethanol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polymer A-1). The molecular weight of the polymer (A-1) was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 20,000.

Production Example II-2: Synthesis of polymer A-2 as the precursor of (A) polyimine Use 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example II-1, except that The reaction was carried out in the same manner as the method described in the above-mentioned Production Example II-1 to obtain a polymer (A-2). The molecular weight of the polymer (A-2) was measured by gel permeation chromatography (in terms of standard polystyrene). As a result, the weight average molecular weight (Mw) was 21,000.

Production Example II-3: Production method of MOI-D (Compound B-1) Add 55.1 g (0.25 mol) of diethylene glycol bis(3-aminopropyl) ether into a separable flask with a capacity of 500 mL, add 150 mL of tetrahydrofuran, and stir at room temperature. Then, the solution obtained by adding 150 mL of tetrahydrofuran to 77.6 g (0.50 mol) of 2-methacryloxyethyl isocyanate (product of Showa Denko Co., Ltd., product name: Karenz MOI) was added to 150 mL of tetrahydrofuran under ice cooling for 30 minutes Add dropwise to the above flask and stir at room temperature for 5 hours. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound B-1.

Production Example II-4: Production method of MOI-AEE (Compound B-7) In the above Production Example II-3, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 26.3 g (0.25 mol) of 2-(2-aminoethoxy)ethanol, and the isocyanate 2-methacrylic acid oxyethyl ester (product of Showa Denko Corporation, product name: Karenz MOI) 77.6 g was replaced with 38.8 g (0.25 mol), except that it was synthesized by the same method as in Production Example II-3 , Compound B-7 was obtained.

Production Example II-5: Production method of MOI-DOA (Compound B-8) In the above production example II-3, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 60.4 g (0.25 mol) of di-n-octylamine, and 2-methylpropene isocyanate Glyoxyethyl (product of Showa Denko Corporation, product name: Karenz MOI) 77.6 g was replaced with 38.8 g (0.25 mol), and except for that, it was synthesized in the same manner as in Production Example II-3 to obtain compound B-8 .

Production Example II-6: (Compound B-11) 2.10 g (0.020 mol) of diethanolamine was added to a three-necked flask with a capacity of 100 mL, 5.6 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. Then, under ice-cooling, a solution obtained by adding 5.6 g of tetrahydrofuran to 2.67 g (0.021 mol) of hexyl isocyanate was dropped into the flask over 15 minutes, and stirred at room temperature for 4 hours. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound B-11.

Examples of raw materials: (Compound B-12) Prepare the compound of compound B-12 as described below.

<Example II-1> Using polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) Polyimide precursor polymer A-1: 100 g, (B) compound preparation example II-3 compound B-1: 8 g, (C) photopolymerization initiator The ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (OXE-02, equivalent In photopolymerization initiator C-1): 3 g, and (G) G-1 compound as a polymerizable unsaturated monomer having 3 or more polymerizable functional groups: 8 g dissolved in γ-butyrolactone ：120 g and dimethyl sulfoxide: 30 g in a mixture. Furthermore, a small amount of γ-butyrolactone is added to adjust the viscosity of the obtained solution to about 30 poises to prepare a negative photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 2.

<Examples II-2 to II-7, Comparative Example II-1> Except for preparing at the compounding ratio shown in Table 2, a negative photosensitive resin composition was prepared in the same manner as in Example II-1, and evaluated according to the above-mentioned method. The results are shown in Table 2.

[化60]

[化61]

[化62]

[化63]

The compounds described in Table 2 (B-1, 7, 8, 11, 12), photopolymerization initiator (C-1), and polymerizable unsaturated monomers having 3 or more polymerizable functional groups (G -1 to G-2) are the following compounds, respectively. [化59]

[化60]

[化61]

[化62]

[化63]

C-1: Ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (trade name : IRGACURE OXE-02(OXE-02)) G-1: pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd., acrylic acid equivalent: 88 g/mol) G-2: Trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd., acrylic acid equivalent: 99 g/mol)

[Table 2] Example Comparative example II-1 II-2 II-3 II-4 II-5 II-6 II-7 II-1 polymer* A-1 100 100 A-2 100 100 100 100 100 100 Compound* B-1 8 8 8 8 B-7 8 B-8 8 B-11 8 B-12 8 Photopolymerization initiator* C-1 3 3 3 3 3 3 3 3 Polymerizable unsaturated monomer* G-1 8 8 8 8 8 8 G-2 8 8 Hardening temperature (℃) 180 180 180 180 180 180 180 180 Adhesion test with sealing material B B B B A B A D Crack test △ △ 〇 〇 〇 〇 〇 X Storage stability A B A B A A A C *Unit: g

＜The third aspect (III)＞

Production Example III-1: (A) Synthesis of polyimide precursor (polymer A-1) Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a separable flask with a capacity of 2 liters, add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone 400 ml, while stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the exotherm caused by the reaction is over, it is left to cool to room temperature, and then it is left to stand for 16 hours.

Then, under cooling in an ice bath, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, and then, A suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added and stirred over 60 minutes. After further stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and dried in a vacuum, thereby obtaining a powdery polymer A-1. The weight average molecular weight (Mw) of the polymer A-1 was measured, and the result was 20,000. Mw/Mn is 1.7. The i-ray absorbance of a 0.1 wt% NMP solution of the polymer was 0.18.

Production Example III-2: Synthesis of Polyimide Precursor (Polymer A-2) In the above production example III-1, 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. In addition, with The reaction was carried out in the same manner as described in Production Example III-1 to obtain polymer A-2. The weight average molecular weight (Mw) of the polymer A-2 was measured and the result was 22,000. Mw/Mn is 1.8. The i-ray absorbance of a 0.1 wt% NMP solution of the polymer was 1.2.

Production Example III-3: Synthesis of polyimide precursor (polymer A-3) ODPA (21.2 g, dried at 140°C for 12 hours before use), HEMA (18.1 g), hydroquinone (0.05) g), pyridine (23.9 g), and diethylene glycol dimethyl ether (150 mL) were mixed, and stirred at a temperature of 60°C for 2 hours to produce the diester of ODPA and HEMA. Then, the reaction mixture was cooled to -10°C, and SOCl ₂ (17.1 g) was added over 1 hour while maintaining the temperature at -10±4°C. After the reaction mixture was diluted with 50 mL of NMP, the solution obtained by dissolving DADPE (11.7 g) in 100 mL of NMP was added dropwise over 1 hour while keeping the mixture at -10±4°C, and the mixture was stirred for 2 hours. Then, it was poured into 6 L of water to precipitate the polyimide precursor, and the mixture of water and polyimine precursor was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor was filtered out, poured into 4 L of water again, stirred for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45°C for 3 days to obtain polymer A-3. The weight average molecular weight (Mw) of the polymer A-3 was measured, and the result was 16,000. Mw/Mn is 2.1. The i-ray absorbance of a 0.1 wt% NMP solution of the polymer was 0.08.

Production Example III-4: Synthesis of Polyimide Precursor (Polymer A-4) In the above Production Example III-3, except that 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (30.4 g) was used instead of ODPA, the reaction was carried out in the same manner as in Production Example III-3 , Thereby obtaining polymer A-4. The weight average molecular weight (Mw) of the polymer A-4 was measured and the result was 23,000. Mw/Mn is 2.2. The i-ray absorbance of a 0.1 wt% NMP solution of the polymer was 0.07.

Production Example III-5: Production method of MOI-D (Compound B-1) Add 55.1 g (0.25 mol) of diethylene glycol bis(3-aminopropyl) ether into a separable flask with a capacity of 500 mL, and add 150 mL of tetrahydrofuran, and stir at room temperature. Then, the solution obtained by adding 150 mL of tetrahydrofuran to 77.6 g (0.50 mol) of 2-methacryloxyethyl isocyanate (product of Showa Denko Co., Ltd., product name: Karenz MOI) was added to 150 mL of tetrahydrofuran under ice cooling for 30 minutes Add dropwise to the above flask and keep stirring at room temperature for 5 hours. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound B-1.

Production Example III-6: Production method of MOI-AEE (Compound B-7) In the above production example III-5, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 26.3 g (0.25 mol) of 2-(2-aminoethoxy)ethanol, and the isocyanate 2-methacrylic acid oxyethyl ester (product of Showa Denko Co., Ltd., product name: Karenz MOI) 77.6 g was replaced with 38.8 g (0.25 mol), except that it was synthesized by the same method as in Production Example III-5 , And obtain compound B-7.

Production Example III-7: Production method of MOI-DOA (Compound B-8) In the above production example III-5, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 60.4 g (0.25 mol) of di-n-octylamine, and 2-methylpropene isocyanate Except that 77.6 g of oxyethyl ester (product of Showa Denko Corporation, product name: Karenz MOI) was replaced with 38.8 g (0.25 mol), the compound was synthesized in the same manner as in Production Example III-5 to obtain compound B- 8.

Production Example III-8: (Compound B-11) Add 2.10 g (0.020 mol) of diethanolamine into a 100 mL three-necked flask, and add 5.6 g of tetrahydrofuran, and stir at room temperature. Then, the solution obtained by adding 5.6 g of tetrahydrofuran to 2.67 g (0.021 mol) of hexyl isocyanate was added dropwise to the flask over 15 minutes under ice-cooling, and stirring was continued for 4 hours at room temperature. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound B-11.

<Example III-1> Using polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) Polyimide precursor polymer A-1: 100 g, (B) Compound B-1 of Production Example III-5: 6 g, and (C) photopolymerization starter The ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (OXE-02, Corresponding to photopolymerization initiator C-1): 3 g is dissolved in a mixture of γ-butyrolactone: 120 g and dimethyl sulfoxide: 30 g. Furthermore, a small amount of γ-butyrolactone is added to adjust the viscosity of the obtained solution to about 30 poises to prepare a negative photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 3.

<Examples III-2 to III-7, Comparative Example III-1> Except for preparing at the compounding ratio shown in Table 3, a negative photosensitive resin composition was prepared in the same manner as in Example III-1, and evaluated according to the above-mentioned method. The results are shown in Table 3.

[化65]

The compounds (B-1, 7, 8, 11) and the photopolymerization initiator (C-1) described in Table 3 are the following compounds, respectively. [化64]

[化65]

C-1: Ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (trade name : IRGACURE OXE-02(OXE-02))

[table 3] Example Comparative example III-1 III-2 III-3 III-4 III-5 III-6 III-7 III-1 polymer* A-1 100 90 A-2 10 A-3 100 100 100 100 100 A-4 100 Compound* B-1 6 6 6 6 B-7 6 B-8 6 B-11 6 Photopolymerization initiator* C-1 3 3 3 3 3 3 3 3 i-ray absorbance 0.18 0.28 0.08 0.07 0.08 0.08 0.08 0.08 Dispersion (Mw/Mn) 1.7 1.7 2.1 2.2 2.1 2.1 2.1 2.1 Hardening temperature (℃) 180 180 180 180 180 180 180 180 Adhesion test with sealing material C C B B A B A D Crack test △ △ 〇 〇 〇 〇 〇 X Elongation after HTS (%) twenty four 14 40 38 36 30 36 8 *Unit: g

<Fourth aspect: Measurement and evaluation method> (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used in the measurement is the brand name "Shodex 805M/806M series" manufactured by Showa Denko Co., Ltd., and the standard monodisperse polystyrene system is selected as "Shodex STANDARD SM-105" manufactured by Showa Denko Co., Ltd. The solvent is N-methyl-2-pyrrolidone, and the detector uses the brand name "Shodex RI-930" manufactured by Showa Denko Co., Ltd.

(2) Determination of free chlorine content of resin composition After the photosensitive resin composition was prepared, it was allowed to stand at room temperature (23.0°C±0.5°C, relative humidity 50%±10%) for 3 days, and then the free chlorine content of the resin composition was measured. The ion concentration measurement was performed at 23.0°C using ThermoFicher's ICS-3000. Based on the measurement results, the content of chloride ions in the resin composition was determined under the following measurement conditions. Weigh 2 g of the photosensitive resin composition, add it to 4 mL of NMP, and stir the resultant with a shaker for 10 minutes to dissolve it. Furthermore, 30 mL of ion-exchanged water was added and stirred with a shaker for 10 minutes, and the insoluble matter was removed by a centrifugal separator (CF15RN manufactured by Himac) and filtered using a disc filter (JP050AN manufactured by DISMIC). . The processed sample solution is automatically introduced into the column 1 mL by the autosampler. ・Protection column for anion analysis: IonPac AS4A-SC (4 mm×250 mm) ・Protection string pump flow rate: 0.500 mL/min ・Separation column for anion analysis: IonPac AS4A-SZ (4 mm×50 mm) ・Sample introduction pipeline pump flow rate: 0.500 mL/min ・Anion chemical suppressor: ACRS-500 (for 4 mm)

(3) Determination of free chlorine content of hardened polyimide film The photosensitive resin composition was spin-coated on a 6-inch silicon wafer so that the cured film thickness became about 10 μm, and heated at 110° C. for 180 seconds on a hot plate to obtain a cured polyimide coating film. The film thickness was measured using Lambda ACE (manufactured by Dainippon Screen Co., Ltd.) as a film thickness measuring device. The free chlorine content of the obtained polyimide coating film was measured under the following measurement conditions. Weigh 2 g of the polyimide film, add it to 4 mL of NMP, and stir the resultant with a shaker for 10 minutes to dissolve it. Furthermore, 30 mL of ion-exchanged water was added and stirred with a shaker for 10 minutes, and the insoluble matter was removed by a centrifugal separator (CF15RN manufactured by Himac) and filtered using a disc filter (JP050AN manufactured by DISMIC). . The processed sample solution is automatically introduced into the column 1 mL by the autosampler. ・Protection column for anion analysis: IonPac AS4A-SC (4 mm×250 mm) ・Protection string pump flow rate: 0.500 mL/min ・Separation column for anion analysis: IonPac AS4A-SZ (4 mm×50 mm) ・Sample introduction pipeline pump flow rate: 0.500 mL/min ・Anion chemical suppressor: ACRS-500 (for 4 mm)

(4) The glass transition temperature of the cured polyimide coating film was measured. The photosensitive resin composition was spin-coated on a 6-inch silicon wafer so that the cured film thickness became about 10 μm, and the photosensitive resin composition was applied on a hot plate at 110°C. After pre-baking for 180 seconds, a temperature-increasing program type curing furnace (VF-000 type, manufactured by Koyo Lindberg) was used to heat at 170° C. for 2 hours in a nitrogen atmosphere to obtain a cured polyimide coating film. The film thickness was measured using Lambda ACE (manufactured by Dainippon Screen Co., Ltd.) as a film thickness measuring device. The obtained polyimide coating film is taken out in short strips, and the load is 200 g/mm ² , the temperature rise rate is 10°C/min, and the temperature range is 20 to 500°C by using a thermomechanical testing device (TMA manufactured by Shimadzu Corporation). -50) The measurement is performed, and the glass transition temperature (Tg) is defined as the intersection of the tangent line of the thermal yield point of the polyimide film in the measurement graph with the temperature as the horizontal axis and the displacement as the vertical axis.

(5) Measurement of the thermal weight loss temperature (5% weight loss temperature) of the cured polyimide coating film The photosensitive resin composition was spin-coated on a 6-inch silicon wafer so that the cured film thickness became about 10 μm, and then pre-baked on a hot plate at 110°C for 180 seconds, and then used a temperature-rising curing oven (VF-2000 type, manufactured by Koyo Lindberg), heated at 170°C for 2 hours in a nitrogen atmosphere to obtain a cured polyimide coating film. The film thickness was measured using a film thickness measuring device Lambda ACE (manufactured by Dainippon Screen Co., Ltd.). The obtained polyimide coating film was shaved off, and a thermogravimetry device (manufactured by Shimadzu Corporation, TGA-50) was used, and the weight of the film when it reached 170°C when the temperature was raised at 10°C/min from room temperature was measured as 100%. The temperature at which the weight is reduced by 5% (5% weight reduction temperature).

(6) The chemical resistance test of the hardened embossed pattern on Cu was performed on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm), using a sputtering device (L-440S-FHL) Type, CANON ANELVA Co., Ltd.) Sputter Ti with a thickness of 200 nm and Cu with a thickness of 400 nm in sequence. Then, on the wafer, the photosensitive resin composition prepared by the following method was spin-coated using a coating developer (Model D-Spin60A, manufactured by SOKUDO), and dried to form a thickness of 10 μm The coating film. Using a mask with a test pattern, the coating film was irradiated with energy of ^{500 mJ/cm 2 by Prisma GHI (manufactured by Ultratech).} Then, cyclopentanone was used as a developer, and the coating film was spray-developed using a coating developer (Model D-Spin60A, manufactured by SOKUDO), and washed with propylene glycol methyl ether acetate, thereby obtaining the float on Cu. Convex pattern. Using a temperature-raising curing furnace (VF-2000, manufactured by Koyo Lindberg), heat the wafer with the embossed pattern formed on Cu at 170°C for 2 hours in a nitrogen atmosphere, thereby obtaining it on Cu A hardened relief pattern containing resin with a thickness of about 6-7 μm. Put the embossed pattern on the resist peeling film (manufactured by ATMI, product name ST-44, the main component is 2-(2-aminoethoxy)ethanol, 1-cyclohexyl-2-pyrrolidone ) After heating to 50°C, the resultant is immersed in the resulting product for 5 minutes, washed with running water for 30 minutes, and then air-dried. Thereafter, the surface of the film was visually observed with an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage caused by the chemical liquid such as cracks, and the rate of change in film thickness after the chemical liquid treatment. The chemical resistance is evaluated based on the following criteria. Film thickness change rate (%) = (film thickness after chemical solution treatment)-(film pressure before chemical solution treatment)/(film thickness before chemical solution treatment)×100 "Excellent": Film before immersion in chemical solution The film thickness change rate is less than 5% based on the thickness. "Good": Based on the film thickness before the chemical solution immersion, the film thickness change rate is more than 5% and less than 10%. "Pass": The film thickness change rate before the chemical solution immersion Based on the film thickness, the film thickness change rate is more than 10% and less than 15% "Fail": Based on the film thickness before the chemical solution immersion, the film thickness change rate is more than 15%

(7) The resolution of the hardened embossed pattern on Cu is on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm), using a sputtering device (L-440S-FHL type, CANON ANELVA) (Manufactured by the company) Sputter Ti with a thickness of 200 nm and Cu with a thickness of 400 nm in sequence. Then, on the wafer, the photosensitive resin composition prepared by the following method was spin-coated using a coating and developing machine (Model D-Spin60A, manufactured by SOKUDO) and dried to form a thickness of 10 μm.涂膜。 Coating. Using a mask with a test pattern, the coating film was irradiated with energy of ^{500 mJ/cm 2 by Prisma GHI (manufactured by Ultratech).} Then, cyclopentanone was used as a developer, and the coating film was spray-developed using a coating developer (Model D-Spin60A, manufactured by SOKUDO), and washed with propylene glycol methyl ether acetate, thereby obtaining the float on Cu. Convex pattern. Using a temperature-raising curing furnace (Model VF-2000, manufactured by Koyo Lindberg), heat the wafer with the embossed pattern formed on Cu at 170°C for 2 hours in a nitrogen atmosphere to obtain a thickness on the Cu A hardened embossed pattern containing resin with a thickness of about 6-7 μm. Observe the produced relief pattern under an optical microscope to find the minimum opening pattern size. At this time, if the area of the opening of the obtained pattern is more than 1/2 of the opening area of the corresponding pattern mask, it is deemed to have been resolved, and the resolution corresponding to the opening with the smallest area is masked The length of the opening edge of the hood is used as the resolution. "Excellent": The size of the smallest opening pattern is less than 10 μm "Good": The size of the smallest opening pattern is more than 10 μm and less than 14 μm "Pass": The size of the smallest opening pattern is more than 14 μm and less than 18 μm "Unqualified": The minimum opening pattern size is 18 μm or more

(8) Determination of the total chlorine content of the resin composition. After preparing the photosensitive resin composition, let it stand for 3 days at room temperature (23.0℃±0.5℃, relative humidity 50%±10%). The amount of chlorine (the total amount of free chlorine and covalently bonded chlorine) is measured. The photosensitive resin composition is burned and decomposed at 800°C, the decomposed gas is absorbed by the ultrapure water, and the total chlorine content in the resin composition is confirmed by ion chromatography. The ion chromatograph includes IC-1000 manufactured by Dionex and IonPac AS12A (4 mm) column, the washing solution is set to 0.3 mM NaHCO ₃ /2.7 mM Na ₂ CO ₃ aqueous solution, and the measurement is performed at a flow rate of 1.5 mL/min.

＜The fourth aspect (IV)＞

[(A) Manufacturing of polyimide precursors] <Production Example IV-1> Synthesis of polyimide precursor A-1 Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a separable flask with a capacity of 2 L, and add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butane 400 mL of ester was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the exotherm caused by the reaction, the reaction mixture was allowed to cool to room temperature for 16 hours. Then, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture for 40 minutes while being stirred in an ice bath. Then, Stir while adding 93.0 g of 4,4'-oxydiphenylamine (ODA) suspended in 350 mL of γ-butyrolactone over 60 minutes. After further stirring for 2 hours at room temperature, 30 mL of ethanol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polymer A-1). The molecular weight of the polymer (A-1) was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 20,000.

In addition, the weight average molecular weight of the resin obtained in each production example was measured using gel permeation chromatography (GPC) under the following conditions to obtain the weight average molecular weight in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M 2 in series Mobile phase: 0.1 mol/L LiBr/NMP Flow rate: 1 mL/min.

<Production Example IV-2> Synthesis of polyimide precursor A-2 Use 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example IV-1, except Otherwise, the reaction was carried out in the same manner as the method described in Production Example IV-1 above to obtain a polymer (A-2). The molecular weight of the polymer (A-2) was measured by gel permeation chromatography (in terms of standard polystyrene). As a result, the weight average molecular weight (Mw) was 26,000.

<Production Example IV-3> Synthesis of polyimide precursor A-3 Except that 48.7 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) of Production Example IV-1, the reaction was carried out in the same manner as the method described in Production Example IV-1 above to obtain Polymer (A-3). The molecular weight of the polymer (A-3) was measured by gel permeation chromatography (in terms of standard polystyrene). As a result, the weight average molecular weight (Mw) was 24,000.

<Production Example IV-4> Synthesis of polyimide precursor A-4 Use 98.6 g of 4,4'-diamino-2,2'-dimethylbiphenyl instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example IV-1. The reaction was carried out in the same manner as described in Production Example IV-1 to obtain a polymer (A-4). The molecular weight of the polymer (A-4) was measured by gel permeation chromatography (in terms of standard polystyrene). As a result, the weight average molecular weight (Mw) was 26,000.

[(B) Manufacturing of compound] <Production Example IV-5> Synthesis of epoxy (meth)acrylate compound I-1 Put 34.0 g of bisphenol A diglycidyl ether into a separable flask with a capacity of 1 L, add 0.4 g of dimethylaniline, 0.04 g of p-methoxyphenol, and 15.5 g of methacrylic acid, and make it at 100°C. Wait for the reaction. After confirming the progress of the reaction by measuring the acid value, it was mixed with 40.5 g of ion exchange resin IRA96SB and stirred overnight, and the process of separating and removing the ion exchange resin by filtration was repeated three times, thereby obtaining a {[propane-2,2- Diylbis(4,1-phenylene)]bis(oxy)}bis(2-hydroxypropane-3,1-diyl)=dimethacrylate as the main component I-1.

<Production Example IV-6> Synthesis of epoxy (meth)acrylate compound I-2 Except that 13.0 g of acrylic acid was used instead of 15.5 g of methacrylic acid, the reaction was carried out in the same manner as the method described in Production Example IV-5 above to obtain {[propane-2,2-diylbis(4,1-extended Phenyl)]bis(oxy)}bis(2-hydroxypropane-3,1-diyl)=I-2 of diacrylate as the main component.

<Production Example IV-7> Synthesis of epoxy (meth)acrylate compound I-3 Except that 17.42 g of ethylene glycol diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, the reaction was carried out in the same manner as described in Production Example IV-5 above to obtain 1,2-bis(3 -Methacryloxy-2-hydroxypropoxy) ethane as the main component I-3.

<Production Example IV-8> Synthesis of epoxy (meth)acrylate compound I-4 Except that 17.42 g of ethylene glycol diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, and 13.0 g of acrylic acid was used instead of 15.5 g of methacrylic acid, the same procedure was followed as described in Production Example IV-5 above. By reaction, I-4 with 1,2-bis(3-propenyloxy-2-hydroxypropoxy)ethane as the main component is obtained.

<Production Example IV-9> Synthesis of epoxy (meth)acrylate compound I-5 Except that 23.23 g of glycerol diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, the reaction was carried out in the same manner as the method described in Production Example IV-5 above to obtain glycerol 1,3-glycerol alkyd. Dimethacrylate is the main component of I-5.

<Production Example IV-10> Synthesis of epoxy (meth)acrylate compound I-6 Except that 23.23 g of glycerol diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, and 13.0 g of acrylic acid was used instead of 15.5 g of methacrylic acid, the reaction was carried out in the same manner as described in Production Example IV-5. Obtained I-6 with glycerin 1,3-diglyceryl alkyd diacrylate as the main component.

<Production Example IV-11> Synthesis of epoxy (meth)acrylate compound I-7 Except that 31.24 g of bisphenol F epoxy resin was used instead of 34.0 g of bisphenol A diglycidyl ether, the reaction was carried out in the same manner as the method described in Production Example IV-5 above to obtain bis[pair (3-methyl 2-hydroxypropoxy-2-hydroxypropoxy)phenyl)]] methane as the main component of I-7.

<Production Example IV-12> Synthesis of epoxy (meth)acrylate compound I-8 Except that 15.02 g of glycidyl phenyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, the reaction was carried out in the same manner as the method described in Production Example IV-5 above to obtain 2-hydroxy-3 methacrylic acid. -Phenoxypropyl ester is the main component of I-8.

<Production Example IV-13> Synthesis of epoxy (meth)acrylate compound I-9 Except that 15.02 g of glycidyl phenyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, and 13.0 g of acrylic acid was used instead of 15.5 g of methacrylic acid, the reaction was carried out in the same manner as described in Production Example IV-5 above. , To obtain I-9 with 2-hydroxy-3-phenoxypropyl acrylate as the main component.

<Production Example IV-14> Synthesis of epoxy (meth)acrylate compound I-10 Except that 35.3 g of bisphenol A diglycidyl ether hydride was used instead of 34.0 g of bisphenol A diglycidyl ether, the reaction was carried out in the same manner as described in Production Example IV-5 above to obtain 2,2-bis [4-(2-Hydroxy-3-methacryloxy-1-propoxy)phenyl]propane I-10 as the main component.

<Production Example IV-15> Synthesis of epoxy (meth)acrylate compound I-11 Use 46.25 g of 9,9-bis[4-(2-glycidylethoxy)phenyl] chrysene instead of 34.0 g of bisphenol A diglycidyl ether. In addition, the same as described in the above production example IV-5 The reaction was carried out in the same manner to obtain I-11 having 4,4'-(9-extensyl)bis(2-hydroxy-3-phenoxypropyl methacrylate) as the main component.

<Production Example IV-16> Synthesis of epoxy (meth)acrylate compound I-12 Except that 24.30 g of 1,6-bis(glycidyloxy)naphthalene was used instead of 34.0 g of bisphenol A diglycidyl ether, the reaction was carried out in the same manner as described in Production Example IV-5 above to obtain 1, 6-bis(3-methacryloxy-2-hydroxypropoxy)naphthalene is I-12 as the main component.

<Production Example IV-17> Synthesis of epoxy (meth)acrylate compound I-13 Put 34.0 g of bisphenol A diglycidyl ether into a separable flask with a capacity of 1 L, add 0.4 g of dimethylaniline, 0.04 g of p-methoxyphenol, and 17.4 g of methacrylic acid, and make it at 100°C. reaction. Confirm the reaction progress by measuring the acid value, without removing the free chlorine by ion exchange resin, to obtain {[propane-2,2-diylbis(4,1-phenylene)]bis(oxy)} Bis(2-hydroxypropane-3,1-diyl)=I-13 which is the main component of dimethacrylate.

[Production of photosensitive resin composition] <Example IV-1> Using the polyimide precursor A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. A-1 as the precursor of (A) polyimide: 100 g, I-1 as (I) epoxy (meth)acrylate compound: 10 g, and (C) photopolymerization initiator 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (hereinafter referred to as C-1 or PDO): 5 g, and tetraethylenedione as (F) monomer Alcohol dimethacrylate (hereinafter referred to as F-1 or M4G): 5 g dissolved in (D) γ-butyrolactone (hereinafter referred to as D-1 or GBL): 100 g. Furthermore, a small amount of GBL was added to adjust the viscosity of the obtained solution to about 40 poises to prepare a negative photosensitive resin composition. Adjust (J) the amount of free chlorine in the photosensitive resin composition, the total amount of chlorine, and the amount of free chlorine contained in the cured film according to the above steps. The composition was evaluated by the above-mentioned methods in sequence. The results are shown in Table 4.

<Examples IV-2 to IV-18, Comparative Examples IV-1 to IV-4> Except that it prepared with the compounding ratio shown in Table 4 or Table 5, it carried out similarly to Example IV-1, and prepared the negative photosensitive resin composition, and performed the same evaluation as Example IV-1. The results are shown in Tables 4 and 5.

[Table 4] Example IV-1 IV-2 IV-3 IV-4 IV-5 IV-6 IV-7 IV-8 IV-9 IV-10 IV-11 (A) Polyimide precursor (g) A-1 100 100 100 100 100 100 100 100 100 100 100 A-2 A-3 A-4 (I) Epoxy (meth)acrylate compound (g) I-1 10 I-2 10 I-3 10 I-4 10 I-5 10 I-6 10 I-7 10 I-8 10 I-9 10 I-10 10 I-11 10 I-12 I-13 (C) Photopolymerization initiator (g) C-1 3 3 3 3 3 3 3 3 3 3 3 (D) Solvent (g) D-1 200 200 200 200 200 200 200 200 200 200 200 (F) Monomer (g) F-1 5 5 5 5 5 5 5 5 5 5 5 (J) Free chlorine in the composition (ppm) 0.2 0.2 1.9 1.9 2 2 0.1 1.5 1.5 0.2 0.3 (J) Total chlorine in the composition (ppm) 15 15 220 220 210 210 15 200 200 15 200 (J) Free chlorine in coating film (ppm) 0.5 0.5 4.4 4.4 4.6 4.6 0.2 3.5 3.5 0.5 0.7 Glass transition temperature (℃) 210 205 205 200 205 200 210 200 195 210 220 5% weight reduction temperature (℃) 300 300 310 310 310 310 300 300 300 300 300 Resolution excellent excellent excellent good good good qualified excellent good good good Chemical resistance excellent excellent excellent excellent excellent excellent excellent qualified qualified excellent excellent

[table 5] Example Comparative example IV-12 IV-13 IV-14 IV-15 IV-16 IV-17 IV-18 IV-1 IV-2 IV-3 IV-4 (A) Polyimide precursor (g) A-1 100 100 100 100 100 100 100 100 A-2 100 A-3 100 A-4 100 (I) Epoxy (meth)acrylate compound (g) I-1 4 25 10 10 10 10 I-2 I-3 I-4 I-5 I-6 I-7 I-8 I-9 I-10 I-11 I-12 10 I-13 10 (C) Photopolymerization initiator (g) C-1 3 3 3 3 3 3 3 3 3 3 3 (D) Solvent (g) D-1 200 200 200 200 200 200 200 200 200 200 200 (F) Monomer (g) F-1 5 5 5 5 5 5 10 5 5 25 10 (J) Free chlorine in the composition (ppm) 0.15 0.08 0.5 0.2 0.2 0.2 0.2 0 500 0 0 (J) Total chlorine in the composition (ppm) 200 7 38 15 15 15 15 0 300 0 0 (J) Free chlorine in coating film (ppm) 0.4 0.2 1.1 0.5 0.5 0.5 0.5 0 1000 0 0 Glass transition temperature (℃) 220 195 220 220 220 220 210 170 210 200 185 5% weight reduction temperature (℃) 300 295 300 300 300 300 300 260 300 300 280 Resolution excellent excellent good qualified qualified qualified good excellent good Unqualified qualified Chemical resistance excellent qualified excellent excellent excellent excellent excellent Unqualified Unqualified excellent Unqualified

According to Tables 4 and 5, the glass transition temperature of the photosensitive resin composition of Example IV-1 is 210°C, the 5% weight loss temperature is 300°C, the resolution is "excellent", and the chemical resistance test result is "excellent" ". Similarly, the photosensitive resin compositions of Examples IV-2 to IV-10 have a glass transition temperature of 195°C or higher, a 5% weight loss temperature of 290°C or higher, and the result of the resolution is "pass" or higher, and chemical resistance The result of the test is "pass" or higher.

In contrast, in Comparative Example IV-1, although the resolution is "excellent", the glass transition temperature is 170°C, and the 5% weight loss temperature is 260°C. As a result of the chemical resistance test, based on the film thickness before immersion, the film thickness change rate changed by 20%, and it was evaluated as "unacceptable". In Comparative Example IV-2, although the glass transition temperature was 210°C, the 5% weight loss temperature was 300°C, and the resolution was "good", the chemical resistance changed by 15%, and it was evaluated as "unacceptable". In Comparative Example IV-3, although the glass transition temperature was 200°C and the 5% weight loss temperature was 300°C, the resolution was "unacceptable." In Comparative Example IV-4, the chemical resistance was "unacceptable".

<Fifth aspect: Measurement and evaluation method> (1) Weight average molecular weight Using gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) of each resin was measured under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ String: Shodex KD-806M manufactured by Showa Denko Co., Ltd., 2 in series, or Shodex 805M/806M series manufactured by Showa Denko Co., Ltd. Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd. Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL/min.

(2) The hardened embossed pattern on Cu is made on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm), using a sputtering device (L-440S-FHL type, CANON ANELVA) (Manufactured by the company) Sputter Ti with a thickness of 200 nm and Cu with a thickness of 400 nm in sequence. Then, on the wafer, the photosensitive resin composition prepared by the following method was spin-coated using a coating and developing machine (Model D-Spin60A, manufactured by SOKUDO), and the photosensitive resin composition prepared by the following method was preliminarily performed on a hot plate at 110°C for 180 seconds. Bake to form a coating film with a thickness of about 4.5 μm. Using a mask with a test pattern, Prisma GHI (manufactured by Ultratech) was used to irradiate the coating film with an energy of ^{100 to 1300 mJ/cm 2 with i-rays.} Next, cyclopentanone was used as a developer, and the coating film was spray-developed by using a coating developer (D-Spin60A, manufactured by SOKUDO) to multiply the time until the unexposed part was completely dissolved and disappeared by 1.4. The coating film was developed using propylene glycol. The methyl ether acetate is sprayed and rinsed by rotating for 10 seconds, thereby obtaining the embossed pattern on Cu.

Using a temperature-increasing program curing furnace (model VF-2000, manufactured by Koyo Lindberg), the wafer with the embossed pattern formed on Cu was heated for 2 hours at the temperature described in Table 1 in a nitrogen environment, thereby A hardened relief pattern containing resin with a thickness of about 3 μm is obtained on Cu.

(3) Standard TMAH solution contact with hardened embossed pattern The hardened embossed pattern made by the method of (2) above is immersed in the standard TMAH solution heated to 50°C for 10 minutes, washed with running water for 30 minutes and air-dried. The standard TMAH solution is mixed as follows Than mixed. Dimethyl sulfide (DMSO): 97.62% by mass Tetramethylammonium hydroxide pentahydrate (TMAH): 2.38% by mass Measure the film thickness before and after the standard TMAH solution contact, and calculate the change amount (dissolved amount) of the film thickness.

(4) Reheat treatment of hardened embossed patterns after contact with standard TMAH solution Using a temperature-rising program curing furnace (model VF-2000, manufactured by Koyo Lindberg), heat treatment for 2 hours on the hardened relief pattern that has been contacted with the standard TMAH solution using the method (3) above in a nitrogen environment. This treatment is performed at the same temperature as the first treatment temperature.

(5) IR measurement An ATR-FTIR measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) was used to measure the above-mentioned cured embossed pattern resin portion using Si 稜鏡. The value obtained by dividing the peak intensity of 1380 cm ^-1 by the peak intensity of 1500 cm ^-1 is used as the imidization index, and the imidization index of the cured film of each example and comparative example is divided by the corresponding resin The composition was cured at 350°C for 2 hours to obtain the imidization index of the film, and the obtained value was calculated as the imidization rate. In addition, ^{the IR peak intensity around 1778 cm -1} when normalized by the IR peak intensity of ^{1500 cm -1 was} also calculated. Regarding the peak intensity at each wavelength, the wavelength with the ^{highest intensity among 10 cm -1} before and after the recorded wavelength is taken as the peak intensity of each wavelength. That is, for example, a peak intensity of 1500 cm ^-1 line intensity of the maximum of the wavelength of 1490 ~ 1510 cm ^-1 as a peak intensity of 1500 cm ^-1.

(6) Measurement of in-plane uniformity Using a coating developer (Model D-Spin60A, manufactured by SOKUDO), spin-coat the photosensitive resin composition used in (2) above on the hardened embossed pattern, using a hot plate at 110°C for 180 seconds Pre-baked. The rotation speed during coating was adjusted so that the film thickness of the coating part formed on the resin of the hardened relief pattern became approximately 6.0 μm. With the boundary between the resin part and the Cu part formed in the lower layer as the center, the surface profiler (P-15: manufactured by KLA Tenkor) was used to measure the coating film formed on the hardened relief pattern within a range of 6000 μm. Film thickness. The in-plane uniformity is obtained from the following equation. In-plane uniformity=[(Maximum film thickness)-(Minimum film thickness)/(Average film thickness of measuring part)] The results were evaluated based on the following criteria. A: In-plane uniformity is less than 0.6 B: In-plane uniformity is 0.6 or more and less than 0.8 C: In-plane uniformity 0.8 or more and less than 1.0 D: In-plane uniformity 1.0 or more

＜The fifth aspect (V)＞

＜Synthesis example of (A) polyimide precursor and (K) urea compound＞ Production Example V-1: (A) Synthesis of polyimide precursor A-1 Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a separable flask with a capacity of 2 L, and add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butane 400 mL of ester was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the exotherm caused by the reaction, the reaction mixture was allowed to cool to room temperature for 16 hours.

Then, under cooling in an ice bath, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture while stirring for 20 minutes, and then , And stirring was performed while adding 93.0 g of 4,4'-oxydiphenylamine (ODA) suspended in 350 mL of γ-butyrolactone over 30 minutes. After further stirring for 4 hours at room temperature, 30 mL of ethanol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polyimide precursor A- 1). The molecular weight of the polyimide precursor A-1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.

Production Example V-2: (A) Synthesis of polyimide precursor A-2 Use 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example V-1, except Otherwise, the reaction was carried out in the same manner as in the method described in Production Example V-1 to obtain a polymer (polyimide precursor A-2). The molecular weight of the polyimide precursor A-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 24,000.

Production Example V-3: (A) Synthesis of polyimide precursor A-3 ODPA 124.0 g and BPDA 29.4 g were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example V-1, except that the method described in Production Example V-1 above was the same The reaction proceeds to obtain a polymer (polyimide precursor A-2). The molecular weight of the polyimide precursor A-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 24,000.

Production Example V-4: (A) Synthesis of polyimide precursor A-4 Use 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example V-1. Otherwise The reaction was carried out in the same manner as the method described in the above-mentioned Production Example V-1 to obtain a polymer (A-2). The molecular weight of the polymer (A-2) was measured by gel permeation chromatography (in terms of standard polystyrene). As a result, the weight average molecular weight (Mw) was 21,000.

Production Example V-5: (K) Synthesis of Urea Compound K-1 Add 55.1 g (0.25 mol) of diethylene glycol bis(3-aminopropyl) ether into a separable flask with a capacity of 500 mL, add 150 mL of tetrahydrofuran, and stir at room temperature.

Then, under ice-cooling, a solution obtained by adding 150 mL of tetrahydrofuran to 77.6 g (0.50 mol) of 2-methacryloxyethyl isocyanate (product of Showa Denko Co., Ltd., product name: Karenz MOI) was added for 30 Minutes were added dropwise to the above flask and stirred at room temperature for 5 hours. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound K-1.

Production Example V-6: (K) Synthesis of Urea Compound K-2 In the above production example V-5, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 26.3 g (0.25 mol) of diethanolamine, and 2-methacryloxyethyl isocyanate (Product of Showa Denko Corporation, product name: Karenz MOI) Except for replacing 77.6 g with 38.8 g (0.25 mol), it was synthesized in the same manner as in Production Example V-5 to obtain compound K-2.

Production Example V-7: (K) Synthesis of Urea Compound K-3 In the above production example V-5, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 60.4 g (0.25 mol) of di-n-octylamine, and 2-methylpropene isocyanate Glyoxyethyl (product of Showa Denko Corporation, product name: Karenz MOI) 77.6 g was replaced with 38.8 g (0.25 mol), and except for that, it was synthesized by the same method as in Production Example V-5 to obtain compound K-3 .

Production Example V-8: (K) Synthesis of Urea Compound K-4 Add 26.3 g (0.25 mol) of diethanolamine to a 500 mL separable flask, and add 150 mL of tetrahydrofuran, and stir at room temperature.

Then, under ice-cooling, 59.8 g (0.25 mol) of 1,1-(bisacryloxymethyl)ethyl isocyanate (product of Showa Denko Co., Ltd., product name: Karenz BEI) was added with 150 mL of tetrahydrofuran The resulting solution was dropped into the flask over 30 minutes, and stirred at room temperature for 5 hours. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound K-4.

Production Example V-9: (K) Synthesis of Urea Compound K-5 In the above Production Example V-6, 38.8 g (0.25 mol) of 2-methacryloxyethyl isocyanate (product of Showa Denko Corporation, product name: Karenz MOI) was replaced with hexyl isocyanate (Tokyo Except for 31.8 g (0.25 mol) of Chemical Industry Co., Ltd., it was synthesized in the same manner as in Production Example V-6 to obtain compound K-5.

<Example V-1> Using the polyimide precursor A-1, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. Dissolve A-1 as a precursor of (A) polyimide: 100 g, C-1 as a sensitizer: 2 g, and K-1 as (K) a urea compound: 15 g in γ- Butyrolactone (hereinafter referred to as GBL): 100 g. Furthermore, a small amount of GBL was added to adjust the viscosity of the obtained solution to about 40 poises to prepare a photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 6.

<Examples V-2 to V-13, Comparative Examples V-1 to V-3> Except for preparing at the compounding ratio shown in Table 6, a photosensitive resin composition was prepared in the same manner as in Example V-1, and the same evaluation as in Example V-1 was performed. The results are shown in Table 6. (C1) Sensitizer C-1, C-2, (K) Urea Compounds K-1～K-6, (D) Photopolymerizable Unsaturated Monomer D-1, (E) Hot Alkali described in Table 6 The generator E-1 is shown below, respectively.

C-1: PBG305 (manufactured by Changzhou Qiangli Company) C-2: PBG3057 (manufactured by Changzhou Qiangli Company)

K-1: The compound described in Production Example V-5 [Chemical Formula 66]

K-2: The compound described in Production Example V-6 [Chemical Formula 67]

K-3: The compound described in Production Example V-7 [Chemical 68]

K-4: The compound described in Production Example V-8 [Chemical 69]

K-5: The compound described in Production Example V-9 [Chemical 70]

K-6: 1,3-Dimethylurea (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-1: NK Ester 4G (manufactured by Shin Nakamura Chemical Co., Ltd.) E-1: 1-(Third-butoxycarbonyl)-4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Table 6] Example Comparative example V-1 V-2 V-3 V-4 V-5 V-6 V-7 V-8 V-9 V-10 V-11 V-12 V-13 V-1 V-2 V-3 (A) Polyimide precursor A-1 100 50 A-2 50 A-3 100 100 100 100 100 100 100 100 100 100 100 100 100 A-4 100 (C1) Sensitive material C-1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 C-2 2 (K) Urea compounds K-1 15 K-2 15 15 15 15 15 15 5 30 15 K-3 15 K-4 15 K-5 15 K-6 3 (D) Photopolymerizable unsaturated monomer D-1 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 (E) Hot alkali generator E-1 5 Heating contact temperature (℃) 170 170 170 170 170 170 170 170 170 170 170 170 170 170 170 230 Imidization rate (%) 90 83 86 84 80 94 72 99 80 81 77 83 93 50 55 100 Change in film thickness when standard TMAH solution is in contact (nm) 344 596 487 472 683 449 965 210 428 566 511 503 290 ＞3000 2530 110 Peak intensity before contact 0.16 0.15 0.15 0.15 0.14 0.17 0.13 0.18 0.14 0.15 0.14 0.15 1.91 0.09 0.10 0.18 Peak intensity after contact 0.07 0.03 0.05 0.06 0.03 0.07 0.01 0.10 0.06 0.04 0.05 0.06 1.10 - 0.12 0.17 Peak intensity after contact/peak intensity before contact 0.41 0.20 0.31 0.37 0.18 0.41 0.11 0.56 0.40 0.27 0.34 0.38 0.58 - 1.20 0.94 Peak intensity after reheating 0.16 0.14 0.14 0.15 0.12 0.17 0.13 0.18 0.11 0.10 0.13 0.16 1.90 - 0.13 0.18 In-plane uniformity B A B B A B A C B B B B A Unable to implement D D

As shown in Table 6, regarding the photosensitive resin composition of Example V-1, the IR peak intensity around 1778 cm ^{-1 is normalized with the IR peak intensity of 1500 cm -1} after contact peak intensity/pre-contact peak The intensity ratio was 0.45, and the in-plane uniformity was evaluated as B. The average strength ratio of the photosensitive resin compositions of Examples V-2 to V-13 was in the range of 0.1 to 0.8, and the evaluation of in-plane uniformity was all results of C or higher. In addition, the imidization rate was all 70% or more, and the peak intensity before the chemical solution contact and the peak intensity after reheating were higher than the peak intensity after the chemical solution contact. The change in film thickness (dissolved amount) when the chemical solution is in contact is 1000 nm or less.

In Comparative Example V-1, the amount of dissolution upon contact with the chemical solution was large, and the film disappeared. In Comparative Example V-2, the amount of dissolution when the chemical liquid is in contact is relatively large, and the value exceeds 1000 nm. In addition, the peak intensity ratio was 1.20, and the in-plane uniformity was evaluated as D. In Comparative Example V-3, there was almost no change in the IR peak intensity machine before and after the chemical solution contact. As a result, the intensity ratio exceeded 0.9, and the evaluation result of the in-plane uniformity was D. [Industrial availability]

By using the photosensitive resin composition of the present invention, the cured film treated at a low temperature can maintain a higher resolution, and the glass transition temperature and 5% weight loss temperature can be increased, thereby improving chemical resistance, and/or by A cured embossed pattern with excellent in-plane uniformity can be obtained by contacting the chemical liquid. By using the negative photosensitive resin composition of the present invention, the adhesion to the sealing material and the storage stability are good, and the in-plane uniformity and crack resistance are excellent when the multilayer is made, and the elongation after the reliability test The rate is excellent. Therefore, the present invention is suitably used, for example, in the field of photosensitive materials that can be used to manufacture electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (21)

A negative photosensitive resin composition comprising: (A) a polyimide precursor having a structural unit represented by the following general formula (1): [化1]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ and R ₂ is at least one of the following general formula (2) as the monovalent organic group represented by: [Chemical formula 2]

(In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group with a carbon number of 1 to 3, and m ₁ is an integer of 2 to 10)}; (B) includes selected from amino formic acid At least one compound from the group consisting of an ester bond and a urea bond; (C) a photopolymerization initiator; and (D) selected from the group consisting of 3-methoxy-N,N-dimethylpropanamide, And at least one solvent in the group consisting of 3-butoxy-N,N-dimethylpropanamide. The negative photosensitive resin composition according to claim 1, wherein the compound (B) is a compound having a urea bond. The negative photosensitive resin composition of claim 1 or 2, wherein the compound (B) is a compound represented by the following general formula (3) or (4): [化3]

{In the formula, R ₇ and R ₈ are each independently a monovalent organic group with 1 to 20 carbon atoms that may contain a hetero atom, and R ₉ and R ₁₀ are each independently a hydrogen atom or a carbon number that may contain a hetero atom 1 ~20 monovalent organic groups} [Chemical 4]

{In the formula, R ₁₁ and R ₁₂ are each independently a monovalent organic group with _{1 to 20 carbons that may contain a hetero atom, and R 13} is a divalent organic group with 1 to 20 carbons that may contain a hetero atom}. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (B) includes at least one selected from the group consisting of (meth)acrylic groups, hydroxyl groups, and amino groups Functional group. The negative photosensitive resin composition according to any one of claims 1 to 4, wherein Y ₁ in the general formula (1) of the polyimide precursor (A) is represented by the following general formula (5) Structure: [化5]

{In the formula, R ₁₄ and R ₁₅ are each independently a hydrogen atom, or a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom}. The negative photosensitive resin composition according to any one of claims 1 to 5, which further contains (E) a rust inhibitor. The negative photosensitive resin composition according to claim 6, wherein the above-mentioned (E) rust inhibitor contains a nitrogen-containing heterocyclic compound. The negative photosensitive resin composition according to claim 7, wherein the nitrogen-containing heterocyclic compound is an azole compound. The negative photosensitive resin composition according to claim 7, wherein the nitrogen-containing heterocyclic compound is a purine or a purine derivative. The negative photosensitive resin composition according to any one of claims 1 to 9, which further contains (F) a silane coupling agent. The negative photosensitive resin composition according to any one of claims 1 to 10, wherein X ₁ in the general formula (1) of the (A) polyimide precursor is selected from the following general formula (20a The structure of at least one of the group consisting of ), (20b), and (20c): [化6]

{In the formula, R ₆ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and l is selected from 0 to Integer in 2} [to 7]

{In the formula, R _{6 is} each independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorinated hydrocarbon group with 1 to 10 carbons, and m is each independently Ground is an integer selected from 0～3} [化8]

{In the formula, R _{6 is} each independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorinated hydrocarbon group with 1 to 10 carbons, and m is each independently Ground is an integer selected from 0 to 3}. The negative photosensitive resin composition according to any one of claims 1 to 11, which comprises: The above (A) polyimide precursor; The compound (B) is 0.1-30 parts by mass based on 100 parts by mass of the polyimide precursor of (A); The (C) photopolymerization initiator, which is 0.1-20 parts by mass based on 100 parts by mass of the polyimide precursor of (A); The (D) solvent is 10 to 1000 parts by mass based on 100 parts by mass of the (A) polyimide precursor. A negative photosensitive resin composition comprising: (A) a polyimide precursor having a structural unit represented by the following general formula (1): [化9]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ and R ₂ is at least one of the following general formula (2) as the monovalent organic group represented by: [formula 10]

(In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group with a carbon number of 1 to 3, and m ₁ is an integer of 2 to 10)}; (B) includes selected from amino formic acid At least one compound in the group consisting of an ester bond and a urea bond; (C) a photopolymerization initiator; and (G) a polymerizable unsaturated monomer having 3 or more polymerizable functional groups. A negative photosensitive resin composition comprising: (A) a polyimide precursor having a structural unit represented by the following general formula (1): [化11]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ and R ₂ is at least one of the following general formula (2) as the monovalent organic group represented by: [formula 12]

(In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group with a carbon number of 1 to 3, and m ₁ is an integer of 2 to 10)}; (B) includes selected from amino formic acid At least one compound in the group consisting of an ester bond and a urea bond; (C) a photopolymerization initiator; and (D1) a solvent, and the above-mentioned (A) polyimide precursor 0.1 wt% N- The i-ray absorbance of the methylpyrrolidone (NMP) solution is 0.03-0.3. A method for producing polyimide, comprising: converting the (A) polyimide precursor contained in the negative photosensitive resin composition of any one of claims 1 to 14 into polyimide Amine step. A method for manufacturing hardened embossed patterns, which includes: (1) The step of coating the negative photosensitive resin composition according to any one of claims 1 to 14 on a substrate to form a photosensitive resin layer on the substrate; (2) The step of exposing the above-mentioned photosensitive resin layer; (3) The step of developing the above-mentioned photosensitive resin layer after exposure to form a relief pattern; and (4) A step of heat-treating the above-mentioned embossed pattern to form a hardened embossed pattern. A photosensitive resin composition comprising: (A1) Polyimide precursor, (I) Compounds having hydroxyl groups and polymerizable unsaturated bonds, (C1) Sensitizer, (D2) Solvent, (J1) free chlorine, and The amount of the free chlorine is 0.0001 to 2 ppm based on the total mass of the photosensitive resin composition. A photosensitive resin composition comprising (A1) Polyimide precursor, (I) Compounds having hydroxyl groups and polymerizable unsaturated bonds, (C1) Sensitizer, (D2) Solvent, (J1) free chlorine, and The photosensitive resin composition is applied to the substrate by the spin method so that the film thickness after curing becomes about 10 μm, and the photosensitive resin composition is cured by heating at 110°C for 180 seconds on a hot plate. The amount of free chlorine contained in the coating film is 0.0001 to 5 ppm based on the total mass of the coating film. A photosensitive resin composition comprising (A1) Polyimide precursor, (I) A compound having a hydroxyl group and a plurality of polymerizable unsaturated bonds, (C1) Sensitizer, (D2) Solvent, (J1) free chlorine and/or (J2) covalently bonded chlorine, and After adjusting the photosensitive resin composition and leaving it to stand at 23°C±0.5°C and a relative humidity of 50%±10% for 3 days, the total amount of chlorine in the photosensitive resin composition is equal to that of the photosensitive resin composition. The total mass is used as a reference and is 0.0001 to 250 ppm. A photosensitive resin composition comprising (A2) at least one resin selected from the group consisting of polyimide and polyimide precursors, (C1) a photosensitizer, and (K) a urea compound, The photosensitive resin composition is cured by heating the photosensitive resin composition at 170°C for 2 hours, and the resulting cured film is formed with tetramethylammonium hydroxide pentahydrate (TMAH) at a temperature of 50°C and a concentration of 2.38% by mass. ^{When the DMSO solution is contacted for 10 minutes, the IR peak intensity around 1778 cm -1} when the above-mentioned cured film before and after the contact is normalized to the IR peak intensity of ^{1500 cm -1} satisfies the following formula ( 1): 0.1≦(peak intensity after contact/peak intensity before contact)≦0.8 (1). A cured film in which when the cured film is contacted with a DMSO solution of TMAH at a temperature of 50°C and a concentration of 2.38% by mass for 10 minutes, the above-mentioned cured film before and after the contact is normalized with an IR peak intensity of ^{1500 cm -1} The IR peak intensity near 1778 cm ^-1 satisfies the following formula (1): 0.1≦(peak intensity after contact/peak intensity before contact)≦0.8 (1).